Electroluminescent metal complex

ABSTRACT

Metal complexes of the formula I or I′ [LDH] n M[L] m  (I) [LTH](M[L] p ) 2  (I1) wherein n is an integer 1 or 2, m and p each is an integer 1 or 2, the sum (n+m) being 2 or 3, M is a metal with an atomic weight of greater than 40 such as Iridium, L is a ligand as described in claim  1 , and LDH is a bidentate ligand of the formula I1 and LTH is a dimer of LDH, binding to 2 metal atoms M, of the formula II′ wherein W is selected from O, S, NR 4 , CR 5 R 6 , X is N or CR 7 , Y is selected from O, S, NR 8 ; and further residues are as defined in claim  1 , show good light emitting efficiency in electroluminescent applications.

The present invention relates to novel electroluminescent metalcomplexes, new intermediates (ligands) for their preparation, electronicdevices comprising the metal complexes, and their use in electronicdevices, especially organic light emitting diodes (OLEDs), as oxygensensitive indicators, as phosphorescent indicators in bioassays, and ascatalysts.

Organic electronic devices that emit light, such as light-emittingdiodes that make up displays, are present in many different kinds ofelectronic equipment. In all such devices, an organic active layer issandwiched between two electrical contact layers. At least one of theelectrical contact layers is light-transmitting so that light can passthrough the electrical contact layer. The organic active layer emitslight through the light-transmitting electrical contact layer uponapplication of a voltage across the contact layers.

Organic electroluminescent compounds known for use as the activecomponent in a light-emitting diode include metal complexes containingchelate ligands binding to the central metal atom via a carbon and anitrogen atom (C,N-binding bidentate ligand; see, for example,[benzo]triazole ligands as of WO06/000544) or certain carbene ligands(C,C-binding) as disclosed in WO06/067074. Complexes of this class mayfurther contain certain heteroatom-binding ligands such as thoseselected from derivatives of acetylacetonate, pyridylcarboxylate,1,1-bipyridine. Related ligand structures are also disclosed inUS-2004-065544, WO05/106868, U.S. Pat. No. 6,420,057.

It has now been found that a certain class of heteroatom-bindingbidentate ligands is especially useful for the preparation ofelectroluminescent metal complexes when combined with another (C,N-and/or C,C-binding) type of ligand. The invention therefore primarilypertains to a metal complex of the formula I or I′[LDH]_(n)M[L]_(m)  (I)[LTH](M[L]_(p))₂  (I′)whereinn is an integer 1 or 2,m and p each is an integer 1 or 2,the sum (n+m) being 2 or 3,M is a metal with an atomic weight of greater than 40,L independently is a colour emission triggering moiety, consisting of 2monodentate ligands or 1 bidentate ligand other than LDH or LTH;LDH is a bidentate ligand of the formula II

and LTH is a dimer of LDH, binding to 2 metal atoms M, of the formulaII′

whereinW is selected from O, S, NR₄, CR₅R₆,X is N or CR₇,Y is selected from O, S, NR₈;R₁, R₂, R₄, R₅, R₆ independently are H, unsubstituted or substitutedC₁-C₁₈alkyl, unsubstituted or substituted C₂-C₁₈alkenyl, unsubstitutedor substituted C₅-C₁₀aryl, unsubstituted or substitutedC₂-C₁₀heteroaryl, C₁-C₁₈acyl;or R₁, R₂ may stand for a substituent selected from halogen,C₁-C₁₈alkoxy, C₁-C₁₈alkylthio, C₁-C₁₈acyl, C₅-C₁₀aryl, C₃-C₁₂cycloalkyl,C₁-C₁₈acyloxy, C₅-C₁₀aryloxy, C₃-C₁₂cycloalkyloxy, or from the residuesCOR, CH═NR, CH═N—OH, CH═N—OR, COOR, CONHR, CONRR′, CONH—NHR, CONH—NRR′,SO₂R, SO₃R, SO₂NHR, SO₂NRR′, SO₂NH—NHR, SO₂NH—NRR′, S(O)R, S(O)OR,S(O)NHR, S(O)NRR′, S(O)NH—NHR, S(O)NH—NRR′, SiRR′R″, PORR′, PO(OR)R′,PO(OR)₂, PO(NHR)₂, PO(NRR′)₂, CN, NO₂, NHR, NRR′, NH—NHR, NH—NRR′,CONROH;R, R′ and R″ independently are selected from C₁-C₁₂alkyl, C₅-C₁₀aryl,C₃-C₁₂cycloalkyl, preferably from C₁-C₆alkyl, phenyl, cyclopentyl,cyclohexyl;and R may also be hydrogen;or the neighbouring residues R₁ and R₂ form an organic bridging groupcompleting, together with the carbon atoms they are bonding to, acarbocyclic or heterocyclic, non-aromatic or preferably aromatic ring of5 to 7 ring atoms in total, which optionally may be substituted;R₇, if present, together with its neighbouring residue R₃ forms anorganic bridging group completing, with the carbon atoms they arebonding to, a carbocyclic or heterocyclic, non-aromatic or preferablyaromatic ring of 5 to 7 ring atoms in total, which optionally may besubstituted; or R₇ embraces the meanings given for R₄, or is halogen,OR, SR, NRR′, COOR, CONRR′, CN, OCN, SCN, or is C₂-C₅alkynyl,C₃-C₅cycloalkyl, hetero-C₂-C₅cycloalkyl, or C₃-C₅cycloalkenyl, eachunsubstituted or substituted; or R₃ is H, unsubstituted or substitutedC₁-C₁₈alkyl, unsubstituted or substituted C₂-C₁₈alkenyl, unsubstitutedor substituted C₅-C₁₀aryl, unsubstituted or substitutedC₂-C₁₀heteroaryl, C₁-C₁₈acyl, OR, SR, NRR′, or is C₂-C₅alkynyl,C₃-C₅cycloalkyl, hetero-C₂-C₅cycloalkyl or C₃-C₅cycloalkenyl eachunsubstituted or mono- or poly-substituted by COR, COOR, CONRR′, CN,halogen and/or by OR;R′₃ is unsubstituted or substituted C₁-C₁₈alkylene, unsubstituted orsubstituted C₂-C₁₈alkenylene, unsubstituted or substitutedC₅-C₁₀arylene, unsubstituted or substituted C₂-C₁₀heteroarylene,C₂-C₁₈diacylene;R₈ is hydrogen or a substituent.

In typical compounds, L independently is a moiety

consisting of 2 monodentate ligands CyC and/or CyN, or 1 bidentateligand wherein the 2 moieties CyC and CyN, or CyC and CyC, areinterlinked by a chemical bond,CyC is a an organic moiety containing a carbon atom bonding to M, andCyN is a cyclic organic moiety containing a nitrogen atom bonding to M,andLDH is a bidentate ligand of the formula II

and LTH is a dimer of LDH, binding to 2 metal atoms M, of the formulaII′

whereinW is selected from O, S, NR₄, CR₅R₆,X is N or CR₇,Y is selected from O, S, NR₈;R₁, R₂, R₄, R₅, R₆ independently are H, unsubstituted or substitutedC₁-C₁₈alkyl, unsubstituted or substituted C₂-C₁₈alkenyl, unsubstitutedor substituted C₅-C₁₀aryl, unsubstituted or substitutedC₂-C₁₀heteroaryl, C₁-C₁₈acyl;or R₁, R₂ independently may stand for a substituent selected fromhalogen, C₁-C₁₈alkoxy, C₁-C₁₈alkylthio, C₁-C₁₈acyl, C₅-C₁₀aryl,C₃-C₁₂cycloalkyl, C₁-C₁₈acyloxy, C₅-C₁₀aryloxy, C₃-C₁₂cycloalkyloxy, orfrom the residues COR, CH═NR, CH═N—OH, CH═N—OR, COOR, CONHR, CONRR′,CONH—NHR, CONH—NRR′, SO₂R, SO₃R, SO₂NHR, SO₂NRR′, SO₂NH—NHR, SO₂NH—NRR′,S(O)R, S(O)OR, S(O)NHR, S(O)NRR′, S(O)NH—NHR, S(O)NH—NRR′, SiRR′R″,PORR′, PO(OR)R′, PO(OR)₂, PO(NHR)₂, PO(NRR′)₂, CN, NO₂, NHR, NRR′,NH—NHR, NH—NRR′, CONROH;R, R′ and R″ independently are selected from C₁-C₁₂alkyl, C₅-C₁₀aryl,C₃-C₁₂cycloalkyl, preferably from C₁-C₆alkyl, phenyl, cyclopentyl,cyclohexyl;and R may also be hydrogen;or the neighbouring residues R₁ and R₂ form an organic bridging groupcompleting, together with the carbon atoms they are bonding to, acarbocyclic or heterocyclic, non-aromatic or preferably aromatic ring of5 to 7 ring atoms in total, which optionally may be substituted;R₇, if present, together with its neighbouring residue R₃ forms anorganic bridging group completing, with the carbon atoms they arebonding to, a carbocyclic or heterocyclic, non-aromatic or preferablyaromatic ring of 5 to 7 ring atoms in total, which optionally may besubstituted; and in case that W is O, NR₄, CR₅R₆ and/or Y contains anitrogen atom, R₇ also embraces the meanings given for R₄;or R₃ is H, unsubstituted or substituted C₁-C₁₈alkyl, unsubstituted orsubstituted C₂-C₁₈alkenyl, unsubstituted or substituted C₅-C₁₀aryl,unsubstituted or substituted C₂-C₁₀heteroaryl, C₁-C₁₈acyl;R′₃ is unsubstituted or substituted C₁-C₁₈alkylene, unsubstituted orsubstituted C₂-C₁₈alkenylene, unsubstituted or substitutedC₅-C₁₀arylene, unsubstituted or substituted C₂-C₁₀heteroarylene,C₂-C₁₈diacylene;R₈ is hydrogen or a substituent.

The complexes of the invention show a number of advantageous featuressuch as improved efficiency and high quantum yield in electroluminescentapplications.

The moieties CyC and CyN in formula I and I′ may be separate chemicalentities (i.e. monodentate ligands) or preferably may be interconnectedby a chemical bond (thus together forming a bidentate ligand). Ligandsof these classes are well known in the art, see for exampleUS-2004-265633; US-2006-172150; WO04/017043; WO06/067074; and documentsmentioned further above. For example, the moiety CyC may be a ring A,

(alternatively named as ring D, see below) representing an optionallysubstituted aryl group which may contain a heteroatom,or a group C,

representing a ligand is derived from a nucleophilic carbene, which maycontain a heteroatom, and the moiety CyN may be a ring B,

representing an optionally substituted nitrogen containing aryl group,which may contain a further heteroatom. In preferred ligands of theseclasses, 2 rings are interconnected, respectively, to form a bidentateligand of the formula

whereinD is —C(═O)—, or —C(X¹)₂—, wherein X¹ is hydrogen, or C₁₋₄alkyl,especially hydrogen, and y is 0, or 1, especially 0.

“Nucleophilic carbene ligand” in the context of the present inventionmeans typical σ-donor ligands that can substitute classical 2e⁻ donorligands. They can be cyclic or acyclic. They can have no or severaldifferent heteroatoms or several heteroatoms of the same kind. Possiblecarbenes are, for example, diarylcarbenes, cyclic diaminocarbenes,imidazol-2-ylidenes, imidazolidin-2-ylidene, 1,2,4-triazol-3-yildenes,1,3-thiazol-2-ylidenes, acyclic diaminocarbenes, acyclicaminooxycarbenes, acyclic aminothiocarbenes, cyclic diborylcarbenes,acyclic diborylcarbenes, phosphinosilyl-carbenes,phosphinophosphonio-carbenes, sulfenyl-trifluormethylcarbenes,sulfenylpentafluorothiocarbenes etc.

Examples for bidentate ligands of this class include those of theformulae

wherein the open bond indicates the carbon atom bonding to the centralmetal atom, the 2 dots (:) indicate the carbene bonding to metal, and Arstands for an aryl group, e.g. phenyl or substituted phenyl such as2,6-diisopropylphenyl. Further explanations for such carbene-typeligands and examples are given in WO06/067074, see passages from page 5,line 27, to page 11, line 16, which are hereby incorporated byreference.

The metal M is generally a metal M with an atomic weight of greater than40, preferably the metal M is selected from TI, Pb, Bi, In, Sn, Sb, Te,especially Mo, Cr, Mn, Ta, V, Cu, Fe, Ru, Ni, Co, Ir, Pt, Pd, Rh, Re,Os, Ag and Au. More preferably the metal is selected from Ir and Ru aswell as Ag, Au, Pt and Pd, wherein Ir and Pt are most preferred.

If M is Co, or Fe, especially Ir, or Rh, (n+m) is preferably 3,especially where n is 1 and m is 2, and p is preferably 2.

If M is Ni, Rh, or Ru, especially Pd, or Pt, (n+m) is preferably 2 and pis preferably 1.

The above formulae II and II′ only show one of the possibleresonance/tautomeric forms of the novel ligand (“enol-form”), whileother forms are possible as well, such as the one of the followingformula II″ (“keto-form”):

or its dimer corresponding to present formula II′, the predominant formmainly depending on the substitution pattern such as R₃ and X.

The bidentate ligand of the formula II or II″, or the tetradentateligand of the formula II′, usually bonds to the metal atom(s) by the Nand Y atom(s) shown in the above structures. In case that W stands for asulfur atom, however, a bond by the sulfur atom may replace the one bythe nitrogen; corresponding conformations thus includes those of thebelow formulae IIa, IIb and IIc (with lines representing bonds to M,coordination bonds indicated by a dashed line, and electron pair bondsindicated by a straight line):

The term “ligand” is intended to mean a molecule, ion, or atom that isattached to the coordination sphere of a metallic ion. The term“complex”, when used as a noun, is intended to mean a compound having atleast one metallic ion and at least one ligand. The term “group” isintended to mean a part of a compound, such a substituent in an organiccompound or a ligand in a complex. The term “facial” is intended to meanone isomer of a complex, Ma₃b₃, having octahedral geometry, in which thethree “a” groups are all adjacent, i.e. at the corners of one triangularface of the octahedron. The term “meridional” is intended to mean oneisomer of a complex, Ma₃b₃, having octahedral geometry, in which thethree “a” groups occupy three positions such that two are trans to eachother, i.e. the three “a” groups sit in three coplanar positions,forming an arc across the coordination sphere that can be thought of asa meridion. The phrase “adjacent to,” when used to refer to layers in adevice, does not necessarily mean that one layer is immediately next toanother layer. The term “photoactive” refers to any material thatexhibits electroluminescence and/or photosensitivity.

Any carbocyclic or heterocyclic, non-aromatic or preferably aromaticring of 5 to 7 ring atoms in total formed by two neighbouring residuesas an organic bridging group together with their anchor atoms often isselected from aryl, heteroaryl, cycloalkyl, or cycloaliphaticunsaturated moieties as explained below.

Substituents, if present, preferably are selected from halogen,C₁-C₁₈alkoxy, C₁-C₁₈alkyl, C₂-C₁₈alkenyl, C₁-C₁₈alkylthio, C₁-C₁₈acyl,C₅-C₁₀aryl, C₄-C₁₀heteroaryl, C₃-C₁₂cycloalkyl, C₁-C₁₈acyloxy,C₅-C₁₀aryloxy, C₃-C₁₂cycloalkyloxy, or from the residues COR, CH═NR,CH═N—OH, CH═N—OR, COOR, CONHR, CONRR′, CONH—NHR, CONH—NRR′, SO₂R, SO₃R,SO₂NHR, SO₂NRR′, SO₂NH—NHR, SO₂NH—NRR′, S(O)R, S(O)OR, S(O)NHR,S(O)NRR′, S(O)NH—NHR, S(O)NH—NRR′, SiRR′R″, PORR′, PO(OR)R′, PO(OR)₂,PO(NHR)₂, PO(NRR′)₂, CN, NO₂, NHR, NRR′, NH—NHR, NH—NRR′, CONROH;

where R, R′ and R″ independently are selected from C₁-C₁₂alkyl,C₁-C₁₂haloalkyl, C₅-C₁₀aryl, C₃-C₁₂cycloalkyl, preferably fromC₁-C₆alkyl, phenyl, cyclopentyl, cyclohexyl; and R may also be hydrogen.

R₈ may advantageously be selected from hydrogen, C₁-C₁₈alkyl,C₂-C₁₈alkenyl, C₅-C₁₀aryl, C₄-C₁₀heteroaryl, and electron pullingsubstituents such as SO₂R′, SO₃R′, SO₂NHR′, SO₂NRR′, SO₂NH—NHR′,SO₂NH—NRR′, C₁-C₁₈acyl, C₁-C₈haloalkyl, especially SO₂R or C₁-C₄perhaloalkyl such as C₁-C₄ perfluoroalkyl. Preferred R₈ (or R₂₀) areselected from H, SO₂R, COR′, C₁-C₈alkyl, C₂-C₈alkenyl, unsubstituted orsubstituted phenyl, pyridyl; more preferably from H, SO₂—R₁₁, CO—R₁₁,where R₁₁ is C₁-C₁₂alkyl, C₁-C₁₂haloalkyl such as CF₃, phenyl, phenylsubstituted by halogen.

Acyl stands for a residue of a sulfonic acid or especially organiccarboxylic acid, which is formed formally by abstraction of the acid OH;examples are formyl, acetyl, propionyl, benzoyl. Generally, C₁-C₁₈ acylstands for a radical X′—R₁₁, wherein X′ is CO or SO₂ and R₁₁ is selectedfrom monovalent aliphatic or aromatic organic residues, usually frommolecular weight up to 300; for example, R₁₁ may be selected fromC₁-C₁₈alkyl, C₂-C₁₈alkenyl, C₅-C₁₀aryl which may be unsubstituted orsubstituted by C₁-C₈alkyl or halogen or C₁.C₈alkoxy, C₆-C₁₅arylalkylwhich may be unsubstituted or substituted in the aromatic part byC₁-C₈alkyl or halogen or C₁.C₈alkoxy, C₄-C₁₂cycloalkyl, and in case thatX′ is CO, R₁₁ may also be H. Acyl is preferably an aliphatic or aromaticresidue of an organic acid —CO—R₁₁, usually of 1 to 30 carbon atoms,wherein R₁₁ embraces aryl, alkyl, alkenyl, alkynyl, cycloalkyl, each ofwhich may be substituted or unsubstituted and/or interrupted asdescribed elsewhere inter alia for alkyl residues, or R′ may be H (i.e.COR′ being formyl). Preferences consequently are as described for aryl,alkyl etc.; more preferred acyl residues are substituted orunsubstituted benzoyl, substituted or unsubstituted C₁-C₁₇alkanoyl oralkenoyl such as acetyl or propionyl or butanoyl or pentanoyl orhexanoyl, substituted or unsubstituted C₅-C₁₂cycloalkylcarbonyl such ascyclohexylcarbonyl.

The complex of formula I may carry a net charge, which is neutralized bysuitable counterions, or the (formally positive) charge of its centralatom M may be neutralized by the equivalent number of ligands (offormally negative charge), which is preferred.

In preferred complexes of the invention, the central atom M is obtainedfrom a salt of a metal cation of charge 2+ (e.g. Pt2+) or especially 3+(e.g. Ir3+,).

In complexes of special interest, n is 1 and m is 2.

Where aryl (e.g. in C₁-C₁₄-aryl) is used, this preferably comprisesmonocyclic rings or polycyclic ring systems with the highest possiblenumber of double bonds, such as preferably phenyl, naphthyl,anthrachinyl, anthracenyl or fluorenyl. The term aryl mainly embracesC₁-C₁₈aromatic moieties, which may be heterocyclic rings (also denotedas heteroaryl) containing, as part of the ring structure, one or moreheteroatoms mainly selected from O, N and S; hydrocarbon aryl examplesmainly are C₆-C₁₈ including phenyl, naphthyl, anthrachinyl, anthracenyl,fluorenyl, especially phenyl. Heteroaryl such as C₄-C₁₈heteroaryl standsfor an aryl group containing at least one heteroatom, especiallyselected from N, O, S, among the atoms forming the aromatic ring;examples include pyridyl, pyrimidyl, pyridazyl, pyrazyl, thienyl,benzothienyl, pyrryl, furyl, benzofuryl, indyl, carbazolyl,benzotriazolyl, thiazolyl, chinolyl, isochinolyl, triazinyl,tetrahydronaphthyl, thienyl, pyrazolyl, imidazolyl. Preferred areC₄-C₁₈aryl, e.g. selected from phenyl, naphthyl, pyridyl,tetrahydronaphthyl, furyl, thienyl, pyrryl, chinolyl, isochinolyl,anthrachinyl, anthracenyl, phenanthryl, pyrenyl, benzothiazolyl,benzoisothiazolyl, benzothienyl, especially C₆-C₁₀aryl; most preferredis phenyl, naphthyl.

Halogen denotes I, Br, Cl, F, preferably Cl, F, especially F.

Alkyl stands for any acyclic saturated monovalent hydrocarbyl group;alkenyl denotes such a group but containing at least one carbon-carbondouble bond (such as in allyl); similarly, alkynyl denotes such a groupbut containing at least one carbon-carbon triple bond (such as inpropargyl). In case that an alkenyl or alkynyl group contains more thanone double bond, these bonds usually are not cumulated, but may bearranged in an alternating order, such as in —[CH═CH—]_(n) or—[CH═C(CH₃)—]_(n), where n may be, for example, from the range 2-50.Where not defined otherwise, preferred alkyl contains 1-22 carbon atoms;preferred alkenyl and alkinyl each contains 2-22 carbon atoms,especially 3-22 carbon atoms.

Where indicated as interrupted, any alkyl moiety of more than one,especially more than 2 carbon atoms, or such alkyl or alkylene moietieswhich are part of another moiety, may be interrupted by a heterofunctionsuch as O, S, COO, OCNR10, OCOO, OCONR10, NR10CNR10, or NR10, where R10is H, C₁-C₁₂alkyl, C₃-C₁₂cycloalkyl, phenyl. They can be interrupted byone or more of these spacer groups, one group in each case beinginserted, in general, into one carbon-carbon bond, with hetero-heterobonds, for example O—O, S—S, NH—NH, etc., not occurring; if theinterrupted alkyl is additionally substituted, the substituents aregenerally not α to the heteroatom. If two or more interrupting groups ofthe type —O—, —NR10-, —S— occur in one radical, they often areidentical.

The term alkyl, wherever used, thus mainly embraces especiallyuninterrupted and, where appropriate, substituted C₁-C₂₂alkyl such asmethyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl,tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl,1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl,1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl,2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl,decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl,tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl.Alkoxy is alkyl-O—; alkylthio is alkyl-S—.

Haloalkyl denotes alkyl substituted by halogen; this includesperhalogenated alkyl such as perfluoroalkyl, especially C₁-C₄perfluoroalkyl, which is a branched or unbranched radical such as forexample —CF₃, —CF₂CF₃, —CF₂CF₂CF₃, —CF(CF₃)₂, —(CF₂)₃CF₃, and —C(CF₃)₃.

Aralkyl is, within the definitions given, usually selected fromC₇-C₂₄aralkyl radicals, preferably C₇-C₁₅aralkyl radicals, which may besubstituted, such as, for example, benzyl, 2-benzyl-2-propyl,β-phenethyl, α-methylbenzyl, α,α-dimethylbenzyl, ω-phenyl-butyl,ω-phenyl-octyl, ω-phenyl-dodecyl; or phenyl-C₁-C₄alkyl substituted onthe phenyl ring by one to three C₁-C₄alkyl groups, such as, for example,2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2,4-dimethylbenzyl,2,6-dimethylbenzyl or 4-tert-butylbenzyl. or3-methyl-5-(1′,1′,3′,3′-tetramethyl-butyl)-benzyl.

The term alkenyl, wherever used, thus mainly embraces especiallyuninterrupted and, where appropriate, substituted C₂-C₂₂alkyl such asvinyl, allyl, etc.

C₂₋₂₄alkynyl is straight-chain or branched and preferably C₂₋₈alkynyl,which may be unsubstituted or substituted, such as, for example,ethynyl, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl,2-methyl-3-butyn-2-yl, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl,1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn-1-yl,trans-3-methyl-2-penten-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyn-8-yl,1-nonyn-9-yl, 1-decyn-10-yl, or 1-tetracosyn-24-yl.

Aliphatic cyclic moieties include cycloalkyl, aliphatic heterocyclicmoieties, as well as unsaturated variants thereof such as cycloalkenyl.Cycloalkyl such as C₃-C₁₈cycloalkyl, is preferably C₃-C₁₂cycloalkyl orsaid cycloalkyl substituted by one to three C₁-C₄alkyl groups, andincludes cyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl,dimethylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl,trimethylcyclohexyl, tert-butylcyclohexyl, cycloheptyl, cyclooctyl,cyclononyl, cyclodecyl, cyclododecyl, 1-adamantyl, or 2-adamantyl.Cyclohexyl, 1-adamantyl and cyclopentyl are most preferred.C₃-C₁₂cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl,cycloundecyl, cyclododecyl; preferred among these residues areC₃-C₆cycloalkyl as well as cyclododecyl, especially cyclohexyl. Furtherring structures occurring are heterocyclic aliphatic rings usuallycontaining 5 to 7 ring members, among them at least 1, especially 1-3,heteromoieties, usually selected from O, S, NR10, where R10 is asexplained above for interrupting NR10-groups; examples includeC₄-C₁₈cycloalkyl, which is interrupted by S, O, or NR10, such aspiperidyl, tetrahydrofuranyl, piperazinyl and morpholinyl. Unsaturatedvariants may be derived from these structures by abstraction of ahydrogen atom on 2 adjacent ring members with formation of a double bondbetween them; an example for such a moiety is cyclohexenyl.

Alkoxy such as C₁-C₂₄alkoxy is a straight-chain or branched radical,e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy,tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, heptyloxy, octyloxy,isooctyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tetradecyloxy,pentadecyloxy, hexadecyloxy, heptadecyloxy and octadecyloxy.

C₆-C₁₈cycloalkoxy is, for example, cyclopentyloxy, cyclohexyloxy,cycloheptyloxy or cyclooctyloxy, or said cycloalkoxy substituted by oneto three C₁-C₄alkyl, for example, methylcyclopentyloxy,dimethylcyclopentyloxy, methylcyclohexyloxy, dimethylcyclohexyloxy,trimethylcyclohexyloxy, or tert-butylcyclohexyloxy.

C₆-C₂₄aryloxy is typically phenoxy or phenoxy substituted by one tothree C₁-C₄alkyl groups, such as, for example o-, m- or p-methylphenoxy,2,3-dimethylphenoxy, 2,4-dimethylphenoxy, 2,5-dimethylphenoxy,2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy,2-methyl-6-ethylphenoxy, 4-tert-butylphenoxy, 2-ethylphenoxy or2,6-diethylphenoxy.

C₆-C₂₄aralkoxy is typically phenyl-C₁-C₉alkoxy, such as, for example,benzyloxy, α-methylbenzyloxy, α,α-dimethylbenzyloxy or 2-phenylethoxy.

C₁-C₂₄alkylthio radicals are straight-chain or branched alkylthioradicals, such as e.g. methylthio, ethylthio, propylthio, isopropylthio,n-butylthio, isobutylthio, pentylthio, isopentyl-thio, hexylthio,heptylthio, octylthio, decylthio, tetradecylthio, hexadecylthio oroctadecylthio.

Silyl such as SiRR′R″ is preferably Si substituted by two or preferablythree moieties selected from unsubstituted or substituted hydrocarbyl orhydrocarbyloxy (wherein the substituents are preferably other thansubstituted silyl), as defined above, or by unsubstituted or substitutedheteroaryl. In case that Si carries only two substituents, the silylgroup is of the type —SiH(R₂) with R₂ preferably being hydrocarbyl orhydrocarbyloxy. Preferred hydrocarbyl(oxy) are C₁-C₂₀alkyl(oxy),aryl(oxy) such as phenyl(oxy), C₁-C₉alkylphenyl(oxy), where “(oxy)”stands for the optional linker “—O—” which may be present or not. Morepreferred are three C₁-C₂₀-alkyl or -alkoxy substituents, i.e.substituted silyl then is Si(R12)₃ with R12 being C₁-C₂₀-alkyl or-alkoxy, especially three C₁-C₈-alkyl substitutents, such as methyl,ethyl, isopropyl, t-butyl or isobutyl.

In one embodiment, the present invention is directed to metal complexescomprising at least one ligand LDH or LTH as described above and atleast one ligand as described in WO06/067074, such as one of the formula

Ring system B (hereinafter also referred to as pyridyl group, though notlimited to pyridyl) in preferred ligands of this class includes a phenylgroup, a substituted phenyl group, a naphthyl group, a substitutednaphthyl group, a furyl group, a substituted furyl group, a benzofurylgroup, a substituted benzofuryl group, a thienyl group, a substitutedthienyl group, a benzothienyl group, a substituted benzothienyl group,and the like. The substitutent on the substituted phenyl group,substituted naphthyl group, substituted furyl group, substitutedbenzofuryl group, substituted thienyl group, and substitutedbenzothienyl group include C₁-C₂₄alkyl groups, C₂-C₂₄alkenyl groups,C₂-C₂₄alkynyl groups, aryl groups, heteroaryl groups, C₁-C₂₄alkoxygroups, C₁-C₂₄alkylthio groups, a cyano group, C₂-C₂₄acyl groups,C₁-C₂₄alkyloxycarbonyl groups, a nitro group, halogen atoms,alkylenedioxy groups, and the like.

In said embodiment the ligand

is more preferably a group of formula

wherein R⁶, R⁷, R⁸, and R⁹ are independently of each other hydrogen,C₁-C₂₄alkyl, C₂-C₂₄alkenyl, C₂-C₂₄alkynyl, aryl, heteroaryl,C₁-C₂₄alkoxy, C₁-C₂₄alkylthio, cyano, acyl, alkyloxycarbonyl, a nitrogroup, or a halogen atom; ortwo substituents R⁶, R⁷, R⁸, and R⁹, which are adjacent to each other,together form a group

wherein R²⁰⁵, R²⁰⁶, R²⁰⁷ and R²⁰⁸ are independently of each other H, orC₁-C₈alkyl,the ring A represents an optionally substituted aryl or heteroarylgroup; or the ring A may be taken with the pyridyl group binding to thering A to form a ring; the alkyl group, alkenyl group, alkynyl group,aryl group, heteroaryl group, alkoxy group, alkylthio group, acyl group,and alkyloxycarbonyl group represented by R⁶, R⁷, R⁸, and R⁹ may besubstituted.

Another example of a preferred class of ligands L are compounds of theformula

wherein Y is S, O, NR²⁰⁰, wherein R²⁰⁰ is hydrogen, C₁-C₄alkyl,C₂-C₄alkenyl, optionally substituted C₆-C₁₀aryl (especially phenyl),—(CH₂)_(r)—Ar (wherein Ar is an optionally substituted C₆-C₁₀aryl,especially

a group —(CH₂)_(r′)X²⁰, wherein r′ is an integer of 1 to 5, X²⁰ ishalogen (especially F, or Cl), hydroxy, cyano, —O—C₁-C₄alkyl,di(C₁-C₄alkyl)amino, amino, or cyano; a group —(CH₂)_(r)OC(O)(CH₂)r″CH₃,wherein r is 1, or 2, and r″ is 0, or 1;

—NH-Ph, —C(O)CH₃, —CH₂—O—(CH₂)₂—Si(CH₃)₃, or

Another preferred class of ligands L is described in WO06/000544, ofwhich the following can advantageously be used according to the presentinvention:

whereinQ¹ and Q² are independently of each other hydrogen, C₁-C₂₄alkyl, orC₆-C₁₈aryl,A²¹ is hydrogen, halogen, C₁-C₄alkoxy, or C₁-C₄alkyl,A²² is hydrogen, halogen, C₁-C₁₂alkoxy, C₁-C₁₂alkyl, or C₆-C₁₀aryl,A²³ is hydrogen, halogen, C₁-C₁₂alkoxy, C₁-C₁₂alkyl, or C₆-C₁₀aryl,A²⁴ is hydrogen, halogen, C₁-C₄alkoxy, or C₁-C₄alkyl, orA²² and A²³, or A²³ and A²⁴ together form a group

wherein R²⁰⁵, R²⁰⁶, R²⁰⁷ and R²⁰⁸ are independently of each other H,halogen, C₁-C₁₂alkoxy, or C₁-C₁₂alkyl,R⁴² is H, halogen, C₁-C₁₂alkyl, C₁-C₁₂alkoxy, or C₁-C₄ perfluoroalkyl,R⁴³ is H, halogen, C₁-C₁₂alkyl, C₁-C₁₂alkoxy, C₁-C₄ perfluoroalkyl,C₇-C₁₅aralkyl, or C₆-C₁₀aryl,R⁴⁴ is H, halogen, C₁-C₁₂alkyl, C₁-C₁₂alkoxy, C₆-C₁₀aryl, C₇-C₁₅aralkyl,or C₁-C₄ perfluoroalkyl,R⁴⁵ is H, halogen, C₁-C₁₂alkyl, C₁-C₁₂alkoxy, or C₁-C₄ perfluoroalkyl,more especially whereinA²¹ is hydrogen,A²² is hydrogen, C₁-C₁₂alkoxy, C₁-C₁₂alkyl, or phenyl,A²³ is hydrogen, C₁-C₁₂alkoxy, C₁-C₁₂alkyl, or phenyl,A²⁴ is hydrogen, orA²³ and A²⁴, or A²³ and A²⁴ together form a group

wherein R²⁰⁵, R²⁰⁶, R²⁰⁷ and R²⁰⁸ are independently of each other H, orC₁-C₈alkyl,R⁴² is H, F, C₁-C₁₂alkyl, C₁-C₈alkoxy, or C₁-C₄ perfluoroalkyl,R⁴³ is H, F, C₁-C₁₂alkyl, C₁-C₈alkoxy, C₁-C₄ perfluoroalkyl, or phenyl,R⁴⁴ is H, F, C₁-C₁₂alkyl, C₁-C₈alkoxy, or C₁-C₄ perfluoroalkyl, andR⁴⁵ is H, F, C₁-C₁₂alkyl, C₁-C₈alkoxy, or C₁-C₄ perfluoroalkyl.

Further examples for this class of ligands are described in WO06/000544from page 14, line 12, to page 18, line 3, and in the examples on pages21-56 and 67-72 of said document, which passages are hereby incorporatedby reference.

Another preferred class of ligands L is described in patent applicationNo. PCT/EP2006/069803, of which the following can advantageously be usedaccording to the present invention:

whereinn is 0, 1 or 2, especially 1;A¹², A¹⁴, A¹⁶, A²¹, A²², A²³ and A²⁴ are independently of each otherhydrogen, CN, halogen, C₁-C₂₄alkyl, C₁-C₂₄alkoxy, C₁-C₂₄alkylthio,C₁-C₂₄ perfluoroalkyl, C₆-C₁₈aryl, which is optionally substituted by G;—NR²⁵R²⁶, —CONR²⁵R²⁶, or —COOR²⁷, or C₂-C₁₀heteroaryl, which isoptionally substituted by G; or C₅-C₁₂cycloalkyl, C₅-C₁₂cycloalkoxy,C₅-C₁₂cycloalkylthio, each of which is optionally substituted by G;especially a group of formula

or 2 adjacent radicals A¹², A¹⁴; or A¹⁴, A¹⁷; or A¹⁷, A¹⁶; or A²¹, A²²;or A²², A²³; or A²³, A²⁴; or A¹⁸, A²²; or A²³, A¹⁹, bonding to vicinalatoms, together are a group of formula

wherein A⁴¹, A⁴², A⁴³, A⁴⁴, A⁴⁵, A⁴⁶ and A⁴⁷ are independently of eachother H, halogen, CN, C₁-C₂₄alkyl, C₁-C₂₄ perfluoroalkyl, C₁-C₂₄alkoxy,C₁-C₂₄alkylthio, C₆-C₁₈aryl, which may optionally be substituted by G,—NR²⁵R²⁶, —CONR²⁵R²⁶, or —COOR²⁷, or C₂-C₁₀heteroaryl; especially

while each A¹¹, A¹³, A¹⁵, A′²¹, A′²², A′²³ and A′²⁴ independently ishydrogen or C₁-C₂₄alkyl;or 2 adjacent radicals A¹¹, A¹²; A¹³, A¹⁴; A¹⁵, A¹⁶; A′²¹, A²¹; A′²²,A²²; A′²³, A²³; A′²⁴, A²⁴, bonding to the same carbon atom, together are═O or ═NR²⁵ or ═N—OR²⁵ or ═N—OH;E¹ is O, S, or NR²⁵,R²⁵ and R²⁶ are independently of each other C₆-C₁₈aryl, C₇-C₁₈aralkyl,or C₁-C₂₄alkyl, R²⁷ is C₁-C₂₄alkyl, C₆-C₁₈aryl, or C₇-C₁₈aralkyl; andY¹, Y² and Y³ are independently of each other a group of formula

whereinR⁴¹ is the bond to M²,R⁷¹ is the bond to M²,R⁴² is hydrogen, or C₁-C₂₄alkyl, CN, C₁-C₂₄alkyl, which is substitutedby F, halogen, especially F, C₆-C₁₈-aryl, C₆-C₁₈-aryl which issubstituted by C₁-C₁₂alkyl, or C₁-C₈alkoxy,R⁴³ is hydrogen, CN, halogen, especially F, C₁-C₂₄alkyl, which issubstituted by F, C₆-C₁₈aryl, C₆-C₁₈aryl which is substituted byC₁-C₁₂alkyl, or C₁-C₈alkoxy, —CONR²⁵R²⁶, —COOR²⁷,

whereinE² is —S—, —O—, or —NR^(25′)—, wherein R^(25′) is C₁-C₂₄alkyl, orC₆-C₁₀aryl,R¹¹⁰ is H, CN, C₁-C₂₄alkyl, C₁-C₂₄alkoxy, C₁-C₂₄alkylthio, —NR²⁵R²⁶,—CONR²⁵R²⁶, or —COOR²⁷, orR⁴² and R⁴³ are a group of formula

wherein A⁴¹, A⁴², A⁴³, A⁴⁴, A⁴⁵, A⁴⁶ and A⁴⁷ are independently of eachother H, halogen, CN, C₁-C₂₄alkyl, C₁-C₂₄ perfluoroalkyl, C₁-C₂₄alkoxy,C₁-C₂₄alkylthio, C₆-C₁₈aryl, which may optionally be substituted by G,—NR²⁵R²⁶, —CONR²⁵R²⁶ or —COOR²⁷, or C₂-C₁₀heteroaryl; especially

R⁴⁴ is hydrogen, CN or C₁-C₂₄alkyl, C₁-C₂₄alkyl, which is substituted byF, halogen, especially F, C₆-C₁₈-aryl, C₆-C₁₈-aryl which is substitutedby C₁-C₁₂ alkyl, or C₁-C₈alkoxy,R⁴⁵ is hydrogen, CN or C₁-C₂₄alkyl, C₁-C₂₄alkyl, which is substituted byF, halogen, especially F, C₆-C₁₈-aryl, C₆-C₁₈-aryl which is substitutedby C₁-C₁₂ alkyl, or C₁-C₈alkoxy,A^(11′), A^(12′), A^(13′), and A^(14′) are independently of each otherH, halogen, CN, C₁-C₂₄alkyl, C₁-C₂₄alkoxy, C₁-C₂₄alkylthio, —NR²⁵R²⁶,—CONR²⁵R²⁶, or —COOR²⁷,R⁶⁸ and R⁶⁹ are independently of each other C₁-C₂₄alkyl, especiallyC₄-C₁₂alkyl, especially hexyl, heptyl, 2-ethylhexyl, and octyl, whichcan be interrupted by one or two oxygen atoms, R⁷⁰, R⁷², R⁷³, R⁷⁴, R⁷⁵,R⁷⁶, R⁹⁰, R⁹¹, R⁹², and R⁹³ are independently of each other H, halogen,especially F, CN, C₁-C₂₄alkyl, C₆-C₁₀aryl, C₁-C₂₄alkoxy,C₁-C₂₄alkylthio, —NR²⁵R²⁶, —CONR²⁵R²⁶, or —COOR²⁷, wherein R²⁵, R²⁶ andR²⁷ are as defined above and G is C₁-C₁₈alkyl, —OR³⁰⁵, SR³⁰⁵, NR³⁰⁵R³⁰⁶,—CONR³⁰⁵R³⁰⁶, or —CN, wherein R³⁰⁵ and R³⁰⁶ are independently of eachother C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, orC₁-C₁₈alkoxy; C₁-C₁₈alkyl, or C₁-C₁₈alkyl which is interrupted by —O—;or R³⁰⁵ and R³⁰⁶ together form a five or six membered ring such as

Another preferred class of ligands L is a compound of formula

wherein R⁶ is hydrogen, halogen, especially F, or Cl; nitro, C₁-C₄alkyl,C₁-C₄ perfluoroalkyl, C₁-C₄alkoxy, or optionally substituted C₆-C₁₀aryl,especially phenyl, R⁷ is hydrogen, halogen, especially F, or Cl;C₁-C₄alkyl, C₁-C₄ perfluoroalkyl, optionally substituted C₆-C₁₀aryl,especially phenyl, or optionally substituted C₆-C₁₀ perfluoroaryl,especially C₆F₅,R⁸ is hydrogen, C₁-C₄alkyl, C₁-C₈alkoxy, C₁-C₄ perfluoroalkyl,optionally substituted C₆-C₁₀aryl, especially phenyl, or optionallysubstituted C₆-C₁₀ perfluoroaryl, especially C₆F₅,R⁹ is hydrogen, halogen, especially F, or Cl; nitro, cyano, C₁-C₄alkyl,C₁-C₄ perfluoroalkyl, C₁-C₄alkoxy, or optionally substituted C₆-C₁₀aryl,especially phenyl,A¹⁰ is hydrogen, halogen, especially F, or Cl; nitro, cyano, C₁-C₄alkyl,C₂-C₄alkenyl, C₁-C₄ perfluoroalkyl, —O—C₁-C₄ perfluoroalkyl,tri(C₁-C₄alkyl)silanyl, especially tri(methyl)silanyl, optionallysubstituted C₆-C₁₀aryl, especially phenyl, or optionally substitutedC₆-C₁₀ perfluoroaryl, especially C₆F₅,A¹¹ is hydrogen, halogen, especially F, or Cl; nitro, cyano, C₁-C₄alkyl,C₂-C₄alkenyl, C₁-C₄ perfluoroalkyl, —O—C₁-C₄ perfluoroalkyl,tri(C₁-C₄alkyl)silanyl, especially tri(methyl)silanyl, optionallysubstituted C₆-C₁₀aryl, especially phenyl, or optionally substitutedC₆-C₁₀ perfluoroaryl, especially C₆F₅,A¹² is hydrogen, halogen, especially F, or Cl; nitro, hydroxy, mercapto,amino, C₁-C₄alkyl, C₂-C₄alkenyl, C₁-C₄ perfluoroalkyl, C₁-C₄alkoxy,—O—C₁-C₄ perfluoroalkyl, —S—C₁-C₄alkyl, a group —(CH₂)_(r)X²⁰, wherein ris 1, or 2, X²⁰ is halogen, especially F, or Cl; hydroxy, cyano,—O—C₁-C₄alkyl, di(C₁-C₄alkyl)amino, —CO₂X²¹, wherein X²¹ is H, orC₁-C₄alkyl; —CH═CHCO₂X²², wherein X²² is C₁-C₄alkyl; —CH(O), —SO₂X²³,—SOX²³, —N C(O)X²³, —NSO₂X²³, —NHX²³, —N(X²³)₂, wherein X²³ isC₁-C₄alkyl; tri(C₁-C₄alkyl)siloxanyl, optionally substituted—O—C₆-C₁₀aryl, especially phenoxy, cyclohexyl, optionally substitutedC₆-C₁₀aryl, especially phenyl, or optionally substituted C₆-C₁₀perfluoroaryl, especially C₆F₅, andA¹³ is hydrogen, nitro, cyano, C₁-C₄alkyl, C₂-C₄alkenyl, C₁-C₄perfluoroalkyl, —O—C₁-C₄ perfluoroalkyl, tri(C₁-C₄alkyl)silanyl, oroptionally substituted C₆-C₁₀aryl.

Specific examples of L are the following compounds (VI-1) to (VI-53):

Special emphasis among them is given to (VI-1) to (VI-47) as well as tothose of the below examples.

Preferred complexes are of formula (I) or (I′) wherein

L independently is a bidentate ligand

wherein the 2 moieties CyC and CyN, or CyC and CyC, are interlinked by achemical bond,andLDH is a bidentate ligand of the formula II and LTH is a dimer of LDH,binding to 2 metal atoms M, of the formula II′, whereinW is selected from O, S, NR₄, CR₅R₆,X is N or CR₇,Y is selected from O, S, NR₈;R₁, R₂ independently are selected from H, unsubstituted or substitutedC₁-C₁₈alkyl, unsubstituted or substituted C₂-C₁₈alkenyl, unsubstitutedor substituted C₅-C₁₀aryl, unsubstituted or substitutedC₂-C₁₀heteroaryl, C₁-C₁₈acyl, halogen, C₁-C₁₈alkoxy, C₁-C₁₈alkylthio,C₁-C₁₈acyl, C₅-C₁₀aryl, C₃-C₁₂cycloalkyl, C₁-C₁₈acyloxy, C₅-C₁₀aryloxy,C₃-C₁₂cycloalkyloxy, or from the residues COR, CH═NR, CH═N—OH, CH═N—OR,COOR, CONHR, CONRR′, CONH—NHR, CONH—NRR′, SO₂R, SO₃R, SO₂NHR, SO₂NRR′,SO₂NH—NHR, SO₂NH—NRR′, S(O)R, S(O)OR, S(O)NHR, S(O)NRR′, S(O)NH—NHR,S(O)NH—NRR′, SiRR′R″, PORR′, PO(OR)R′, PO(OR)₂, PO(NHR)₂, PO(NRR′)₂, CN,NO₂, NHR, NRR′, NH—NHR, NH—NRR′, CONROH;where R, R′ and R″ independently are selected from C₁-C₁₂alkyl,C₁-C₆haloalkyl, phenyl, cyclopentyl, cyclohexyl; and R may also behydrogen;or the neighbouring residues R₁ and R₂ form an organic bridging groupcompleting, together with the carbon atoms they are bonding to, acarbocyclic or heterocyclic, non-aromatic or preferably aromatic,6-membered ring, which optionally may be substituted;R₄, R₅, R₆ independently are H, unsubstituted or substituted C₁-C₈alkyl,unsubstituted or substituted C₂-C₈alkenyl, unsubstituted or substitutedphenyl;R₇, if present, together with its neighbouring residue R₃ forms anorganic bridging group completing, with the carbon atoms they arebonding to, an aromatic 6-membered ring, which optionally may besubstituted; and in case that W is O, NR₄, CR₅R₆ and/or Y contains anitrogen atom, R₇ also embraces the meanings given for R₄;or R₃ is H, unsubstituted or substituted C₁-C₁₈alkyl, unsubstituted orsubstituted C₂-C₁₈alkenyl, unsubstituted or substituted phenyl,unsubstituted or substituted C₂-C₁₀heteroaryl, C₁-C₁₈acyl; andR′₃ is unsubstituted or substituted C₁-C₈alkylene, unsubstituted orsubstituted C₂-C₈alkenylene, unsubstituted or substituted phenylene,unsubstituted or substituted C₂-C₁₀heteroarylene, C₂-C₈diacylene;R₈ is selected from hydrogen, C₁-C₁₈alkyl, C₂-C₁₈alkenyl, C₅-C₁₀aryl,C₄-C₁₀heteroaryl, and electron pulling substituents such as SO₂R′,SO₃R′, SO₂NHR′, SO₂NRR′, SO₂NH—NHR′, SO₂NH—NRR′, C₁-C₁₈acyl,C₁-C₈haloalkyl;such as those of the formula (I) or (I′) whereinY is O or NR₈;M is selected from TI, Pb, Bi, In, Sn, Sb, Te, Mo, Cr, Mn, Ta, V, Cu,Fe, Ru, Ni, Co, Ir, Pt, Pd, Rh, Re, Os, Ag and Au;R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈ are as defined above and, if substituted,the substituent is selected from halogen, C₁-C₁₂alkoxy, C₁-C₁₂alkylthio,benzoyl substituted by C₁-C₄alkyl or C₁-C₄alkoxy or halogen, benzoyloxysubstituted by C₁-C₄alkyl or C₁-C₄alkoxy or halogen, phenyl, phenyloxy,C₃-C₁₂cycloalkyl, C₃-C₁₂cycloalkyloxy, or from the residues COR, OCOR,COOR, CONHR, CONRR′, SO₂R, SO₃R, SO₂NHR, SO₂NRR′, SiRR′R″, PORR′,PO(OR)R′, PO(OR)₂, CN, NO₂, NHR, NRR′, NH—NHR, NH—NRR′,where R, R′ and R″ independently are selected from C₁-C₁₂alkyl,C₁-C₆haloalkyl, phenyl, cyclopentyl, cyclohexyl; and R may also behydrogen.

More preferred complexes are of the formula I, wherein

n is an integer 1,

M is Co, Fe, or especially Ir, Rh, and m is 2, or

M is Ni, Rh, Ru, or especially Pd, Pt, and m is 1,

R₁, R₂ independently are selected from H, unsubstituted or substitutedC₁-C₈alkyl, unsubstituted or substituted phenyl, halogen, C₁-C₈alkoxy,COR, COOR, SO₂R, CN, NHR, NRR′;

or the neighbouring residues R₁ and R₂ form an organic bridging groupcompleting, together with the carbon atoms they are bonding to, anannellated phenyl ring, which optionally may be substituted;

R₅, R₆ independently are H, unsubstituted or substituted C₁-C₈alkyl,unsubstituted or substituted C₂-C₈alkenyl, unsubstituted or substitutedphenyl;

R₄ is as defined for R₅ or is H;

R₇, if present, together with its neighbouring residue R₃ forms anorganic bridging group completing, with the carbon atoms they arebonding to, a phenyl ring, which optionally may be substituted; and incase that W is O, NR₄, CR₅R₆ and/or Y contains a nitrogen atom, R₇ alsoembraces hydrogen, C₁-C₄alkyl;or R₃ is unsubstituted or substituted C₁-C₈alkyl, unsubstituted orsubstituted C₂-C₈alkenyl, unsubstituted or substituted phenyl; andany substituent, if present, is selected from halogen, C₁-C₈alkyl,C₁-C₈alkoxy, phenyl, phenyloxy, COR, OCOR, COOR, SO₂R, CN, NHR, NRR′;andR, R′ and R″ independently are selected from C₁-C₆alkyl, and R may alsobe hydrogen;R₈ is H, SO₂—R₁₁, CO—R₁₁, where R₁₁ is C₁-C₁₂alkyl, C₁-C₁₂haloalkyl,phenyl, phenyl substituted by halogen.

Of special technical interest are those compounds wherein Y is O.Likewise of technical interest are those compounds wherein R₃ isdifferent from hydrogen.

Examples for some more preferred complexes of the invention are those ofthe formulae

and tautomeric forms thereofwherein

is a bidentate C,N-binding ligand as defined above,n is 1,M is Ir and m is 2 orM is Pt and m is 1;W is O, S, NR₄, CR₅R₆,X is N or CH,Y is O or NR₈;R₁, R₂ independently are selected from H, C₁-C₈alkyl, phenyl, halogen,C₁-C₈alkoxy, CN, NHR, NRR′;or R₁ and R₂ together with the carbon atoms they are bonding to form anannellated phenyl ring, which optionally may be substituted;R₃ is H, unsubstituted or substituted C₁-C₈alkyl, unsubstituted orsubstituted C₂-C₈alkenyl, unsubstituted or substituted phenyl;R₄, R₅, R₆ independently are H or C₁-C₈alkyl;R₈ is H, C₁-C₈alkyl, COR, SO₂R;R₁₃, R₁₄, R₁₅, R₁₆ independently are hydrogen or a substituent; andany substituent, if present, is selected from halogen, C₁-C₈alkyl,C₁-C₈alkoxy, COR, NHR, NRR′; andR, R′ and R″ independently are selected from C₁-C₆alkyl, and R may alsobe hydrogen.

Examples for dimeric complexes of the formula I′ include those of theformula

whereinW, X, Y and the ligands

are as defined above,R₁, R₂ independently are selected from H, unsubstituted or substitutedC₁-C₈alkyl, unsubstituted or substituted phenyl, halogen, C₁-C₈alkoxy,COR, COOR, SO₂R, CN, NHR, NRR′;R′₁ and R′₂, independently, are hydrogen or a substituent, where anysubstituent, if present, is selected from halogen, C₁-C₈alkoxy, phenyl,phenyloxy, COR, OCOR, COOR, SO₂R, CN, NHR, NRR′; andR, R′ and R″ independently are selected from C₁-C₆alkyl, and R may alsobe hydrogen; andR′₃ is unsubstituted or substituted C₁-C₈alkylene, unsubstituted orsubstituted C₂-C₈alkenylene, unsubstituted or substituted phenylene;such as the compound

with n=2.

Conversion of the present metal complexes into suitable layers mayfollow methods known in the art; construction of the electroluminescentdevices containing said layers is well known in the art (see, forexample, WO04/017043, and further documents mentioned above).

Some of the ligands of formula II are known compounds; some of the moreinteresting ligands however are novel. The present invention thereforeincludes compounds of the formula V or VI

or tautomers thereof,wherein R₁, R₂, R₃, W and Y are as defined for the metal complexes ofthe invention;X′ is N, and in case that W is O, NR₄, CR₅R₆ and/or Y contains anitrogen atom, X′ may also stand for CR₁₇;R is C₁-C₁₂alkyl, phenyl, or said phenyl or C₁-C₁₂alkyl substituted byC₁-C₄alkoxy or halogen;at least one of R₁₃, R₁₄, R₁₅, R₁₆ is an electron-pushing substituent,preferably selected from halogen, hydroxy, OR, C₁-C₁₈alkyl,C₁-C₁₈alkoxy, C₁-C₁₈alkylthio, C₁-C₁₈acyloxy, NH—C₁-C₁₈acyl, NR″R′,NH—NR″R′, CONR′OH; especially where one of R₁₃, R₁₄, R₁₅, R₁₆ is anelectron-pushing substituent selected from hydroxy, OR, C₁-C₁₈alkyl,C₁-C₁₈alkoxy, C₁-C₁₈alkylthio, NR″R′;while the remaining of R₁₃, R₁₄, R₁₅, R₁₆, independently, may also beselected from hydrogen or substituents as defined further above, forexample halogen, C₁-C₁₈alkyl, C₁-C₁₈acyl, C₅-C₁₀aryl, C₃-C₁₂cycloalkyl,C₅-C₁₀aryloxy, C₃-C₁₂cycloalkyloxy, or from the residues COR′, CH═NR′,CH═N—OH, CH═N—OR′, COOR′, CONHR′, CONRR′, CONH—NHR′, CONH—NRR′, SO₂R′,SO₃R′, SO₂NHR′, SO₂NRR′, SO₂NH—NHR′, SO₂NH—NRR′, S(O)R, S(O)OR′,S(O)NHR′, S(O)NRR′, S(O)NH—NHR′, S(O)NH—NRR′, SiRR′R″, POR″R′,PO(OR″)R′, PO(OR′)₂, PO(NHR′)₂, PO(NRR′)₂, CN, NO₂, NHR′, NRR′, NH—NHR′,NH—NRR′, CONR′OH, and especially are hydrogen or alkyl;R′ and R″ independently are as defined for R, or are hydrogen;R₁₇ is H, C₁-C₆alkyl, andR₂₀ is an electron pulling residue selected from SO₂R′, SO₃R′, SO₂NHR′,SO₂NRR′, SO₂NH—NHR′, SO₂NH—NRR′, C₁-C₁₈acyl, C₁-C₈haloalkyl, especiallySO₂R or C₁-C₄ perhaloalkyl such as C₁-C₄ perfluoroalkyl.

The preparation of the novel ligands may follow methods known in theart. For example, those ligands wherein X is CR₇, may be obtained inanalogy to methods described in WO05/106868.

Ligands wherein X stands for nitrogen are conveniently prepared startingfrom the corresponding amines

by reaction with an acyl component such as a suitable acid anhydride oracid halogenide R₃—CO-Hal to obtain a ligand wherein Y is O; or byreaction with a suitable nitrile to obtain a ligand wherein Y is NH.

Ligands wherein Y is O may be converted into ligands containing Y as Sin analogy to the procedure described by K. Waisser, Sci. Pharm. 67,1999, 113-122.

Reactions may be carried out in analogy to known methods (see, forexample, Dothager, Robin S.; Putt, Karson S.; Allen, Brittany J.;Leslie, Benjamin J.; Nesterenko, Vitaliy; Hergenrother, Paul J.; J. Am.Chem. Soc. 127 (24), 2005, 8686). Free amino functions may be furthermodified following procedures known in the art to introduce residues R₈other than hydrogen. For example, novel ligands of the sulfonamide class(Y═N—SO₂R such as compounds of the above formula VI) may be obtained byconversion of the corresponding amine (compound of the below formula VIIwith Y═NH) with a suitable halogenide Cl—R₂₀ in analogy to J. Lee etal., J. Med. Chem. 2003, 46, 3116; or in analogy to W. Anderson, Synth.Commun. 19, 1989, 2237-2242; an example is the reaction of a ligand IIor II′, where X is nitrogen, with a sulfochloride Cl—SO₂R:

where “ring” stands for the cyclic moiety

and R₃ may, in the synthesis for compounds of the formula II′, may alsostand for the bridging group R′₃ (dimer, 2 reaction centres converted).

The amine may be obtained, for example in analogy to methods describedin DE-A-2333378. For example, the educts 2-aminothiophenol and4-dimethylamino-2-nitrobenzaldehyde may be reacted to obtain(4-benzothiazol-2-yl-3-nitrophenyl)-dimethylamine, whose nitro group maybe reduced to the amine in a conventional manner (e.g. using SnCl₂/HCl),and the product is reacted with methane sulfochloride.

The metal complexes of the present invention can be prepared fromreadily available salts of the metals and the ligands as described,including the ligands of the present invention of the formula VII

and tautomers thereof, wherein all symbols are as defined above forformulae I and II, according to usual methods known from the prior art;see, for example, WO06/000544 and literature cited therein.

Iridium metal complexes of formula Ir(L^(a))₂L′, where L^(a) and L′independently stand for the 2 classes of bidentate ligands [CyC, CyN]and formula II featured in the present invention, can, for example, beprepared by first preparing an intermediate iridium dimer of formula

wherein X is H or lower alkyl such as methyl or ethyl, and L^(a) is asdefined above, and then addition of HL′. The iridium dimers cangenerally be prepared by first reacting iridium trichloride hydrate withHL^(a) and adding NaX, and by reacting iridium trichloride hydrate withHL^(a) in a suitable solvent, such as 2-ethoxyethanol.

The present invention is also directed to an electronic devicecomprising the metal complex and its fabrication process. The electronicdevice can comprise at least one organic active material positionedbetween two electrical contact layers, wherein at least one of thelayers of the device includes the metallic complex compound. Theelectronic device can comprise an anode layer (a), a cathode layer (e),and an active layer (c). Adjacent to the anode layer (a) is an optionalhole-injecting/transport layer (b), and adjacent to the cathode layer(e) is an optional electron-injection/transport layer (d). Layers (b)and (d) are examples of charge transport layers.

The active layer (c) can comprise at least approximately 1 weightpercent of metal complex of present invention.

In some embodiments, the active layer (c) may be substantially 100% ofthe metal complex because a host charge transporting material, such asAlq₃ (see below) is not needed. By “substantially 100%” it is meant thatthe metal complex is the only material in the layer, with the possibleexception of impurities or adventitious by-products from the process toform the layer. Still, in some embodiments, the metal complex may be adopant within a host material, which is typically used to aid chargetransport within the active layer (c). The active layer (c), includingany of the metal complexes, can be a small molecule active material.

The device may include a support or substrate adjacent to the anodelayer (a) or the cathode layer (e). Most frequently, the support isadjacent the anode layer (a). The support can be flexible or rigid,organic or inorganic. Generally, glass or flexible organic films areused as a support. The anode layer (a) is an electrode that is moreefficient for injecting holes compared to the cathode layer (e). Theanode can include materials containing a metal, mixed metal, alloy,metal oxide or mixed-metal oxide. Suitable metal elements within theanode layer (a) can include the Groups 4, 5, 6, and 8-11 transitionmetals. If the anode layer (a) is to be light transmitting, mixed-metaloxides of Groups 12, 13 and 14 metals, such as indium-tin-oxide, may beused. Some non-limiting, specific examples of materials for anode layer(a) include indium-tin-oxide (“ITO”), aluminum-tin-oxide, gold, silver,copper, nickel, and selenium.

The anode layer (a) may be formed by a chemical or physical vapordeposition process or spin-cast process. Chemical vapor deposition maybe performed as a plasma-enhanced chemical vapor deposition (“PECVD”) ormetal organic chemical vapor deposition (“MOCVD”).

Physical vapor deposition can include all forms of sputtering (e.g., ionbeam sputtering), e-beam evaporation, and resistance evaporation.

Specific forms of physical vapor deposition include rf magnetronsputtering or inductively-coupled plasma physical vapor deposition(“ICP-PVD”). These deposition techniques are well-known within thesemiconductor fabrication arts.

A hole-transport layer (b) may be adjacent the anode. Both holetransporting small molecule compounds and polymers can be used.

Commonly used hole transporting molecules include:N,N′-diphenyl-N,N′-bis(3-methylphenyl)-[1,1′-biphenyl]-4,4′-diamine(TPD), 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC),N,N′-bis(4-methylphenyl)-N,N′-bis(4-ethylphenyl)-[1,1′-(3,3′-dimethyl)biphenyl]-4,4′-diamine(ETPD), tetrakis-(3-methylphenyl)-N,N,N′,N′-2,5-phenylenediamine (PDA),a-phenyl-4-N,N-diphenylaminostyrene (TPS),p-(diethylamino)benzaldehydediphenylhydrazone (DEH), triphenylamine(TPA), bis[4-(N,N-diethylamino)-2-methylphenyl](4-methylphenyl)methane(MPMP),1-phenyl-3-[p-(diethylamino)styryl]-5-[p-(diethylamino)phenyl]pyrazoline(PPR or DEASP), 1,2-trans-bis(9H-carbazol-9-yl)cyclobutane (DCZB),N,N,N′,N′-tetrakis(4-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine (TTB),4,4′-N,N-dicarbazole-biphenyl (CBP),N,N-dicarbazoyl-1,4-dimethene-benzene (DCB), porphyrinic compounds, andcombinations thereof.

Commonly used hole transporting polymers are polyvinylcarbazole,(phenylmethyl) polysilane, poly(3,4-ethylendioxythiophene) (PEDOT), andpolyaniline. Hole-transporting polymers can be obtained by dopinghole-transporting molecules such as those mentioned above into polymerssuch as polystyrene and polycarbonate.

The hole-injection/transport layer (b) can be formed using anyconventional means, including spin-coating, casting, and printing, suchas gravure printing. The layer can also be applied by ink jet printing,thermal patterning, or chemical, or physical vapor deposition.

Usually, the anode layer (a) and the hole-injection/transport layer (b)are patterned during the same lithographic operation. The pattern mayvary as desired. The layers can be formed in a pattern by, for example,positioning a patterned mask or resist on the first flexible compositebarrier structure prior to applying the first electrical contact layermaterial. Alternatively, the layers can be applied as an overall layer(also called blanket deposit) and subsequently patterned using, forexample, a patterned resist layer and wet-chemical or dry-etchingtechniques. Other processes for patterning that are well known in theart can also be used. When the electronic devices are located within anarray, the anode layer (a) and hole injection/transport layer (b)typically are formed into substantially parallel strips having lengthsthat extend in substantially the same direction.

The active layer (c) may comprise the metal complexes described herein.The particular material chosen may depend on the specific application,potentials used during operation, or other factors. The active layer (c)may comprise a host material capable of transporting electrons and/orholes, doped with an emissive material that may trap electrons, holes,and/or excitons, such that excitons relax from the emissive material viaa photoemissive mechanism. Active layer (c) may comprise a singlematerial that combines transport and emissive properties. Whether theemissive material is a dopant or a major constituent, the active layermay comprise other materials, such as dopants that tune the emission ofthe emissive material. Active layer (c) may include a plurality ofemissive materials capable of, in combination, emitting a desiredspectrum of light. Examples of phosphorescent emissive materials includethe metal complexes of the present invention. Examples of fluorescentemissive materials include DCM and DMQA. Examples of host materialsinclude Alq₃, CBP and mCP. Examples of emissive and host materials aredisclosed in U.S. Pat. No. 6,303,238, which is incorporated by referencein its entirety.

The active layer (c) can be applied from solutions by any conventionaltechnique, including spin coating, casting, microgravure coating,roll-coating, wire bar-coating, dip-coating, spray-coating, and printingtechniques such as screen-printing, flexography, offset-printing,gravure-printing and ink-jet printing. The active organic materials mayalso be applied directly by vapor deposition processes, depending uponthe nature of the materials.

The solvent used in the solution processing method is not particularlylimited and preferable are those which can dissolve or uniformlydisperse the materials. Preferably the materials may be dissolved in asolvent, the solution deposited onto a substrate, and the solventremoved to leave a solid film. Any suitable solvents may be used todissolve the ionic compounds, provided it is inert, may dissolve atleast some material and may be removed from the substrate byconventional drying means (e.g. application of heat, reduced pressure,airflow, etc.). Suitable organic solvents include, but are not limitedto, are aromatic or aliphatic hydrocarbons, halogenated such aschlorinated hydrocarbons, esters, ethers, ketones, amide, such aschloroform, dichloroethane, tetrahydrofuran, toluene, xylene, ethylacetate, butyl acetate, methyl ethyl ketone, acetone, dimethylformamide, dichlorobenzene, chlorobenzene, propylene glycol monomethylether acetate (PGMEA), and alcohols, and mixtures thereof. Also waterand mixtures with water miscible solvents are possible.

Optional layer (d) can function both to facilitate electroninjection/transport, and also serve as a buffer layer or confinementlayer to prevent quenching reactions at layer interfaces. Morespecifically, layer (d) may promote electron mobility and reduce thelikelihood of a quenching reaction if layers (c) and (e) would otherwisebe in direct contact. Examples of materials for optional layer (d)include metal-cheated oxinoid compounds (e.g.,tris(8-hydroxyquinolato)aluminum (Alq₃) or the like);phenanthroline-based compounds (e.g.,2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (“DDPA”),4,7-diphenyl-1,10-phenanthroline (“DPA”), or the like; azole compounds(e.g., 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (“PBD”) orthe like, 3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole(“TAZ”) or the like; other similar compounds; or any one or morecombinations thereof. Alternatively, optional layer (d) may be inorganicand comprise BaO, LiF, Li₂O, or the like.

The electron injection/transport layer (d) can be formed using anyconventional means, including spin-coating, casting, and printing, suchas gravure printing. The layer can also be applied by ink jet printing,thermal patterning, or chemical or physical vapor deposition.

The cathode layer (e) is an electrode that is particularly efficient forinjecting electrons or negative charge carriers. The cathode layer (e)can be any metal or nonmetal having a lower work function than the firstelectrical contact layer (in this case, the anode layer (a)). Materialsfor the second electrical contact layer can be selected from alkalimetals of Group 1 (e.g., Li, Na, K, Rb, Cs), the Group 2 (alkalineearth) metals, the Group 12 metals, the rare earths, the lanthanides(e.g., Ce, Sm, Eu, or the like), and the actinides. Materials, such asaluminum, indium, calcium, barium, yttrium, and magnesium, andcombinations thereof, may also be used. Li-containing organometalliccompounds, LiF, and Li₂O can also be deposited between the organic layerand the cathode layer to lower the operating voltage. Specificnon-limiting examples of materials for the cathode layer (e) includebarium, lithium, cerium, cesium, europium, rubidium, yttrium, magnesium,or samarium.

The cathode layer (e) is usually formed by a chemical or physical vapordeposition process. In general, the cathode layer will be patterned, asdiscussed above in reference to the anode layer (a) and optional holeinjecting layer (b). If the device lies within an array, the cathodelayer (e) may be patterned into substantially parallel strips, where thelengths of the cathode layer strips extend in substantially the samedirection and substantially perpendicular to the lengths of the anodelayer strips.

Electronic elements called pixels are formed at the cross points (wherean anode layer strip intersects a cathode layer strip when the array isseen from a plan or top view).

In other embodiments, additional layer (s) may be present within organicelectronic devices. For example, a layer between the hole injectinglayer (b) and the active layer (c) may facilitate positive chargetransport, band-gap matching of the layers, function as a protectivelayer, or the like. Similarly, additional layers between the electroninjecting layer (d) and the cathode layer (e) may facilitate negativecharge transport, band-gap matching between the layers, function as aprotective layer, or the like. Layers that are known in the art can beused. Some or all of the layers may be surface treated to increasecharge carrier transport efficiency. The choice of materials for each ofthe component layers may be determined by balancing the goals ofproviding a device with high device efficiency with the cost ofmanufacturing, manufacturing complexities, or potentially other factors.

The charge transport layers (b) and (d) are generally of the same typeas the materials of the active layer (c). More specifically, if theactive layer (c) has a small molecule compound, then the chargetransport layers (b) and (d), if either or both are present, can have adifferent small molecule compound. If the active layer (c) has apolymer, the charge transport layers (b) and (d), if either or both arepresent, can also have a different polymer. Still, the active layer (c)may be a small molecule compound, and any of its adjacent chargetransport layers may be polymers.

Each functional layer may be made up of more than one layer. Forexample, the cathode layer may comprise a layer of a Group I metal and alayer of aluminum. The Group I metal may lie closer to the active layer(c), and the aluminum may help to protect the Group I metal fromenvironmental contaminants, such as water.

Although not meant to limit, the different layers may have the followingrange of thicknesses: inorganic anode layer (a), usually no greater thanapproximately 500 nm, for example, approximately 50-200 nm; optionalhole-injecting layer (b), usually no greater than approximately 100 nm,for example, approximately 50-200 nm; active layer (c), usually nogreater than approximately 100 nm, for example, approximately 10-80 nm;optional electron-injecting layer (d), usually no greater thanapproximately 100 nm, for example, approximately 10-80 nm; and cathodelayer (e), usually no greater than approximately 1000 nm, for example,approximately 30-500 nm. If the anode layer (a) or the cathode layer (e)needs to transmit at least some light, the thickness of such layer maynot exceed approximately 100 nm.

The location of the electron-hole recombination zone in the device, andthus the emission spectrum of the device, can be affected by therelative thickness of each layer. For example, when a potentiallight-emitting compound, such as Alq₃ is used in the electron transportlayer (d), the electron-hole recombination zone can lie within the Alq₃layer.

The emission would then be that of Alq₃, and not a desired sharpemission. Thus, the thickness of the electron-transport layer should bechosen so that the electron-hole recombination zone lies within thelight-emitting layer (i.e., active layer (c)). The desired ratio oflayer thicknesses can depend on the exact nature of the materials used.

The efficiency of the devices made with metal complexes can be furtherimproved by optimizing the other layers in the device. For example, moreefficient cathodes such as Ca, Ba, Mg/Ag, or LiF/Al can be used. Shapedsubstrates and hole transport materials that result in a reduction inoperating voltage or increase quantum efficiency are also applicable.Additional layers can also be added to tailor the energy levels of thevarious layers and facilitate electroluminescence.

Depending upon the application of the electronic device, the activelayer (c) can be a light-emitting layer that is activated by a signal(such as in a light-emitting diode) or a layer of material that respondsto radiant energy and generates a signal with or without an appliedpotential (such as detectors or voltaic cells). Examples of electronicdevices that may respond to radiant energy are selected fromphotoconductive cells, photoresistors, photoswitches, phototransistors,and phototubes, and photovoltaic cells. After reading thisspecification, skilled artisans will be capable of selecting material(s) that for their particular applications.

The electroluminescent devices may be employed for full color displaypanels in, for example, mobile phones, televisions and personal computerscreens. Accordingly the present invention relates also to a deviceselected from stationary and mobile displays, such as displays forcomputers, mobile phones, laptops, pdas, TV sets, displays in printers,kitchen equipment, billboards, lightings, information boards anddestination boards in trains and buses, containing an organic lightemitting diode according to the present invention.

In OLEDs, electrons and holes, injected from the cathode (e) and anode(a) layers, respectively, into the photoactive layer (c), form negativeand positively charged polarons in the active layer (c). These polaronsmigrate under the influence of the applied electric field, forming apolaron exciton with an oppositely charged species and subsequentlyundergoing radiative recombination. A sufficient potential differencebetween the anode and cathode, usually less than approximately 20 volts,and in some instances no greater than approximately 5 volts, may beapplied to the device. The actual potential difference may depend on theuse of the device in a larger electronic component. In many embodiments,the anode layer (a) is biased to a positive voltage and the cathodelayer (e) is at substantially ground potential or zero volts during theoperation of the electronic device. A battery or other power source (s)may be electrically connected to the electronic device as part of acircuit.

In other embodiments, the metal complex compound can be used as a chargetransport material in layer (b) or (d).

The compound does not need to be in a solid matrix diluent (e.g., hostcharge transport material) when used in layer (b) (c), or (d) in orderto be effective. A layer greater than approximately 1% by weight of themetal complex compound, based on the total weight of the layer, and upto substantially 100% of the complex compound can be used as the activelayer (c). Additional materials can be present in the active layer (c)with the complex compound. For example, a fluorescent dye may be presentto alter the color of emission.

A diluent may also be added. The diluent can be a polymeric material,such as poly(N-vinyl carbazole) and polysilane. It can also be a smallmolecule, such as 4,4′-N,N′-dicarbazole biphenyl or tertiary aromaticamines. When a diluent is used, the complex compound is generallypresent in a small amount, usually less than 20% by weight, preferablyless than 10% by weight, based on the total weight of the layer.

The metallic complexes may be used in applications other than electronicdevices. For example, the complexes may be used as catalysts orindicators (e.g., oxygen-sensitive indicators, phosphorescent indicatorsin bioassays, or the like).

The following examples illustrate certain features and advantages of thepresent invention. They are intended to be illustrative of theinvention, but not limiting. Unless otherwise indicated, all percentagesare by weight, “over night” stands for a time period of 14 to 16 hours,and room temperature denotes a temperature from the range 20-25° C.

ABBREVIATIONS

ITO indium doped tin oxide

Ph phenyl

t- denotes a tertiary (alkyl) group, such as t-Bu standing for tertiarybutyl

Bu butyl

LC liquid chromatography

MS mass spectrometry

CIE International Commission on Illumination/chromaticity

NMR nuclear magnetic resonance, of ¹H if not otherwise indicated

DMSO dimethyl sulfoxide

EXAMPLES A) Ligands Example 1 N-Benzothiazol-2-yl-benzamide

In a 100 ml three-necked flask equipped with magnetic stirrer,thermometer, dropping funnel and nitrogen inlet, 5.34 g (35.6 mmol) of2-amino-benzothiazole are dissolved in 50 ml of pyridine and cooled to3° C. using an ice bath. 5.0 g of benzoylchloride (35.6 mmol) are addeddropwise within 20 minutes, keeping the temperature within the mixturebelow 5° C. Stirring is continued for another 15 minutes, then themixture is poured on 500 ml of water. The white suspension is stirredfor 1 hour, filtered, the white residue is washed 3 times with 100 ml ofwater, respectively, and dried over night at 50° C. and 30 mbar. 7.5 gcrude product obtained are purified by flash-chromatography usinghexane/ethylacetate 3:1 (v/v), yielding 5.8 g of the title product.

¹H-NMR (300 MHz, CDCl₃): 8.02-7.96 (m, 2H), 7.86-7.78 (m, 1H), 7.55-7.48(m, 1H), 7.44-7.36 (m, 2H), 7.30-7.24 (m, 3H)

Examples 2-6

Compounds of the following Tab. 1 are prepared in analogy to example 1using corresponding amines and acid chlorides or anhydrides.

TABLE 1 example ligand characterization (NMR) 2

12.2 (s, 1H) 8.10-8.07 (m, 2H) 7.7-7.50 (m, 5H) 7.05 (dxd, 1H) 3.81 (s,3H) 3

12.65 (s, 1H) 8.00 (d, 2H) 7.61 (d, 1H) 7.35 (d, 1H) 7.00 (dxd, 1H) 6.73(d, 2H) 3.80 (s, 3H) 3.00 (s, 6H) 4

3.97 (q, 2H) 1.26 (t, 3H) 5

10.76 (s, 1H) 7.83 (d, 2H) 6.75 (d, 2H) 4.05 (q, 2H) 3.01 (s, 6H) 1.36(t, 3H) 6

11.19 (s, 1H) 7.99-7.95 (m, 2H) 7.69-7.62 (m, 1H) 7.59-7.54 (m, 2H) 4.10(q, 2H) 1.38 (t, 3H)

Example 7 2,2,2-Trifluoro-N-thiazol-2-yl-acetamide

Into a 250 ml three-necked flask equipped with magnetic stirrer,thermometer, dropping funnel and nitrogen inlet, 5.0 g (49.9 mmol) of2-aminothiazol and 14.3 g (99.85 mmol) of ethyltrifluoroacetate in 100ml of tetrahydrofuran are introduced. A solution of 14.4 g (124.8 mmol)of potassium-t-butylate in 50 ml of tetrahydrofuran is added dropwisewithin 15 minutes to the stirred brown solution, whose internaltemperature is kept in the range 20-25° C. using an ice bath. Stirringis continued for another 75 minutes, then 300 ml of a buffer solution isadded and pH 7 is adjusted by addition of 2N aq. HCl. Extraction with300 ml of ethyl acetate is carried through 3 times, the combined organicphases are washed with 250 250 ml of water, dried over MgSO₄, andfiltered. After evaporating the solvent, the crude product isrecrystallized from 2-propanol, yielding 2.26 g of the title product.

¹H-NMR (300 MHz, DMSO): 7.62 (d, 1H), 7.29 (d, 1H),

Examples 8-10

Compounds of the following Tab. 2 are prepared in analogy to example 7using corresponding amines and esters.

TABLE 2 example ligand characterization (NMR) 8

8.07 (s, 1H) 9

12.84 (s, 1H) 7.58-7.55 (m, 2H) 7.34-7.29 (m, 2H) 3.46 (s, 3H) 10

7.67-7.63 (m, 1H) 7.54-7.48 (m, 1H) 7.43-7.33 (m, 2H)

Example 11 3-[3-Benzooxazol-(2)-yliden]-1,1,1-trifluor-propan-2-one

Into a 500 ml three-necked flask equipped with magnetic stirrer,thermometer, dropping funnel and nitrogen inlet, 14.0 g (125 mmol) ofpotassium-t-butylate in 120 ml of tetrahydrofuran are introduced. Theclear solution is cooled to 3° C. using an ice bath. A solution of 6.65g (50 mmol) 2-methylbenzoxazol and 14.2 g (100 mmol) ofethyltrifluoroacetate in 200 ml of tetrahydrofuran is slowly addedwithin 50 minutes. Stirring at 3° C. is continued for another 60minutes, then the ice bath is removed and the orange coloured solutionis stirred over night at room temperature. Subsequently, 120 ml of anaqueous 10% (w/w) solution of citric acid is added dropwise, and themixture is poured on 1 l of water with stirring. Extraction with 500 mlof ethyl acetate is carried through 3 times, the combined organic phasesare washed 3 times with 100 ml of saturated aq. NaCl, dried over MgSO₄,and filtered. After evaporating the solvent, the residue is washed 2times with 10 ml of ice cooled ethyl acetate, and dried over night at50° C. and 25 mbar, yielding 7.9 g of the title product.

¹H-NMR (300 MHz, DMSO-D₆): 7.62-7.57 (m, 1H), 7.54-7.49 (m, 1H),7.39-7.26 (m, 2H), 5.73 (s, 1H)

Examples 12-14

Compounds of the following Tab. 3 are prepared in analogy to example 11using corresponding methyl compounds.

TABLE 3 characterization example ligand (NMR) 12

7.98 (s, 1H) 7.79 (s, 1H) 5.54 (s, 1H) 4.19 (q, 2H) 1.24 (t, 3H) 13

6.54 (s, 1H) 4.32 (q, 2H) 1.33 (t, 3H) 14

7.11 (d, 1H) 6.98 (d, 1H) 5.28 (s, 1H) 3.59 (s, 3H)

Examples 15 and 16

Compounds of the following Tab. 4 are prepared in analogy to thesynthesis of N-(1,3-benzothiazol-2-yl)-benzamidine described by T.George, Synthesis 1974, 346-347.

TABLE 4 example ligand characterization (NMR) 15

7.95 (d, 2H) 7.80 (d, 1H) 7.67 (d, 1H) 7.33 (dxd, 1H) 7.20 (dxd, 1H)6.75 (d, 2H) 3.00 (s, 6H) 16

9.87 (s, 1H) 9.35 (s, 1H) 8.11 (m, 2H) 7.59-7.50 (m, 4H) 7.28-7.18 (m,3H)

Example 17N-(2-Benzthiazol-2-yl-5-dimethylamino-phenyl)-methanesulfonamid

a) Starting from 2-aminothiophenol and4-dimethylamino-2-nitro-benzaldehyde,(4-benzthiazol-2-yl-3-nitro-phenyl)-dimethylamin is prepared in analogyto the procedure described in example 1 of DE-A-2333378.b) In a 250 ml three-necked flask equipped with magnetic stirrer,thermometer, reflux condenser and nitrogen inlet, 15.25 g of (78.8 mmol)anhydrous tin(II) chloride are dissolved in 40 ml of 37% hydrochloricacid, and 6.94 g (23.2 mmol) of(4-benzthiazol-2-yl-3-nitro-phenyl)-dimethylamin (product of part a) areadded with stirring. The thick, red suspension heats up to 100° C. Theinternal temperature is kept at 60° C. for the following 5 hours. Aftercooling, the reaction mixture is adjusted to pH 14 by addition of 180 mlof a 4N solution of sodium hydroxid, and stirring is continued foranother 30 minutes. After filtration, the residue is washed three timeswith 50 ml of water and dried over night at 50° C. and 25 mbar, yielding6.49 g of crude 4-benzthiazol-2-yl-N,N-dimethyl-benzene-1,3-diamin,which is used for the subsequent step without further purification.c) Into a 250 ml three-necked flask equipped with magnetic stirrer,thermometer and nitrogen inlet, 6.20 g (23.0 mmol) of crude4-benzthiazol-2-yl-N,N-dimethyl-benzene-1,3-diamin (product of part b)in 65 ml of pyridine are introduced and cooled to 3° C. with stirring.3.19 g (27.6 mmol) of methansulfochloride are added dropwise within 30Minuten using a syringe, then the ice bath is removed and the blacksolution is stirred over night at room temperature. The reaction mixtureis then poured dropwise into 700 ml of ice water; the reddish brownsuspension thus obtained is stirred for 20 minutes, filtered, theresidue washed 3 times with 100 ml of ice water, and dried over night at50° C. and 25 mbar. 7.50 g of the title product are obtained.

¹H-NMR (300 MHz, DMSO-D₆): 11.89 (s, 1H), 8.04 (d, 1H), 7.84 (d, 1H),7.70 (d, 1H)

-   -   7.52-7.34 (m, 2H)    -   6.85 (d, 1H)    -   6.59 (dxd, 1H)    -   3.17 (s, 3H)    -   3.03 (s, 6H)

Examples 18 and 19

Compounds of the following Tab. 5 are prepared in analogy to thecompound of example 17.

TABLE 5 characterization example ligand (NMR) 18

11.16 (s, 1H) 7.94 (d, 1H) 7.72-7.69 (m, 2H) 7.37-7.33 (m, 2H) 6.88-6.87(m, 1H) 6.63-6.60 (m, 1H) 3.20 (s, 3H) 3.03 (s, 6H) 19

11.08 (s, 1H) 8.22 (dxd, 1H) 7.88-7.81 (m, 2H) 7.73-7.60 (m, 2H)7.52-7.41 (m, 2H) 7.35-7.29 (m, 1H) 3.25 (s, 3H)

B) Intermediate Complexes

The compounds in Table 6 are prepared according to the method shown inexample 10 of WO 2006/000544.

TABLE 6 Example Structure 20

21

22

23

24

C) Final Complexes

The compounds in Table 7 are prepared according to the method shown inexample 11 of WO 2006/000544.

TABLE 7 Photoluminescence in Toluene Example Dimer of Ligand of λ_(max)[nm] 25 Example 20 Example 1 539 26 Example 20 Example 2 543 27 Example20 Example 3 550 28 Example 20 Example 4 539/565 29 Example 20 Example 5541 30 Example 20 Example 6 540/564 31 Example 20 Example 7 532 32Example 20 Example 8 525/557 33 Example 20 Example 9 538/569 34 Example20 Example 10 530/563 35 Example 20 Example 11 538 36 Example 20 Example12 541 37 Example 20 Example 14 559/587 38 Example 20 Example 15 576 39Example 20 Example 16 559 40 Example 20 Example 17 552 41 Example 20Example 18 577 42 Example 20 Example 19 541 43 Example 20 2-(2- 574Hydroxyphenyl) benzthiazol 44 Example 20 2-(2- 564 Hydroxyphenyl)benzoxazol 45 Example 22 Example 5 516/549 46 Example 22 Example 11 51547 Example 23 Example 5 525/554 48 Example 23 Example 11 517/550 49Example 24 Example 4 501 50 Example 24 Example 5 499 51 Example 24Example 7 458/487 52 Example 24 Example 9 464/497 53 Example 24 Example10 544 54 Example 24 Example 11 544 55 Example 24 2-(2- 589Hydroxyphenyl) benzthiazol 56 Example 24 2-(2- 507/539 Hydroxyphenyl)benzoxazol

Example 57

447 mg (0.186 mmol) of the compound prepared in Example 21, 98 mg (0.372mMol) of silver trifluoromethanesulfonate and 15 ml of 2-nonanone areplaced in a 50 ml three necked round bottomed flask, equipped with amagnetic stirrer and a reflux condenser. The yellow suspension isevacuated and purged with nitrogen three times. The reaction mixture isheated to 100° C. internal temperature for two hours, then to 120° C.for one additional hour and then cooled to 50° C. 95 mg (0.372 mMol) ofthe compound prepared in Example 1 are added to the brown suspension andthe resulting reaction mixture is heated to 120° C. internal temperaturefor 18 hours. The brown suspension is then cooled to room temperature,filtered and the residue washed three times with 20 ml of hexane. Thefiltrate is evaporated and the crude product purified by flashchromatography using Hexane/Ethylacetate=40:1 as eluent. 60 mg of thedesired product are isolated as a yellow powder. The photoluminescencespectrum in toluene shows emission maxima at 507 and 540 nm.

The compounds in Table 8 are prepared according to Example 57:

TABLE 8 Photoluminescence in Example Dimer Ligand Toluene/λ_(max) [nm]58 Example 21 Example 4 508/538 59 Example 21 Example 5 505/540 60Example 21 Example 7 507/538 61 Example 21 Example 8 506/541 62 Example21 Example 9 506/543 63 Example 21 Example 10 507/539 64 Example 21Example 11 508/540 65 Example 21 Example 12 509/540 66 Example 212-(2-Hydroxyphenyl) 535/565 benzthiazol 67 Example 212-(2-Hydroxyphenyl) 515/541 benzoxazol

Further Examples Example 68

The following intermediate complex is prepared in analogy to example 10of WO 2006/000544 using 2-(4-tert.butylphenyl)pyridine as a ligand:

Examples 69-71

The complexes described in Tab. 9 below are prepared in analogy to thosedescribed in Tab. 7.

TABLE 9 Luminiscent complexes from intermediate of example 68Photoluminescence in Example No. Ligand of Toluene λ_(max) [nm] 69Example 7 500/533 70 Example 9 500/535 71 Example 14 512

Application Examples

An organic luminescence device having a single organic light-emittinglayer is prepared in the following manner: On a glass substrate, a 75 nmthick ITO film formed by sputtering and subsequently patterned byoxygen-plasma treatment (commercially available at Thin Film Devices(TFD), USA). Onto the ITO film, a 80 nm thick hole-injection layer usingPEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrene sulfonate);available under the trade name Baytron® P AI 4083) is formed byspin-coating followed by heating at 200° C. (6 minutes). A solution of48 mg of compound prepared in one of the above examples and indicated inthe following Table 9, 468 mg of poly(9-vinylcarbazole) (PVK), 265 mg of2-(4-biphenylyl)-5-(4-tert.butylphenyl)-1,3,4-oxadiazole (PBD) and 220mg of N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine (TPD, CAS-No.65181-78-4) in 46.7 ml of toluene are applied by spin coating (950 rpm.;50 seconds) to obtain a thickness of 80 nm. After the thus-treatedsubstrate has been set in a vacuum deposition chamber, a cathode havinga two-layer electrode structure is formed by depositing 5 nm bariumfollowed by 70 nm aluminum. The following table 10 shows colour data(CIE-data x, y) and efficacy when the device is driven to emit 100cd/sqm luminance, and corresponding current density and voltage.

TABLE 10 Colour (CIE x, y) and light emitting efficacy of device drivenat 100 cd/m² Complex of efficacy current density Example No. CIE x, ycd/A voltage V mA/cm² 25 0.45, 0.53 1.4 8.4 70 26 0.46, 0.52 1.3 8.6 7527 28 0.50, 0.49 2.6 12.4 34 29 0.46, 0.53 1.2 7.2 85 30 0.45, 0.54 0.38.0 337 31 0.44, 0.54 1.0 8.3 104 32 33 0.46, 0.53 1.1 7.4 90 34 0.43,0.55 0.8 9.6 135 35 0.45, 0.53 1.0 7.6 102 36 0.48, 0.51 10 6.3 10 370.51, 0.48 2.0 6.2 51 38 0.53, 0.46 0.8 8.6 133 39 0.51, 0.48 1.4 7.5 7040 41 42 0.48, 0.50 0.4 8.6 256 43 0.52, 0.47 2.9 6.2 34 44 0.52, 0.483.3 5.9 30 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 0.41, 0.54 5.05.6 20 60 0.41, 0.54 3.1 6.5 32 61 62 0.38, 0.56 6.4 5.6 13 63 64 0.42,0.53 2.4 7.1 42 65 0.43, 0.52 5.9 6.1 17 66 67 69 0.29, 0.56 2.1 6.48 4670 0.28, 0.60 3.0 5.52 33 71 0.32, 0.61 1.3 6.6 59

The invention claimed is:
 1. Compound of the formula I or I′[LDH]_(n)M[L]_(m)  (I)[LTH](M[L]_(p))₂  (I′) wherein n is an integer 1 or 2, m and p each isan integer 1 or 2, the sum (n+m) being 2 or 3, M is a metal with anatomic weight of greater than 40, L is a moiety

consisting of 2 monodentate ligands CyC and CyN or CyC and CyC, or 1bidentate ligand other than LDH or LTH, wherein the 2 moieties CyC andCyN, or CyC and CyC, are interlinked by a chemical bond, wherein CyC isan organic moiety containing a carbon atom bonding to M, and CyN is acyclic organic moiety containing a nitrogen atom bonding to M; LDH is abidentate ligand of the formula II

and LTH is a dimer of LDH, binding to 2 metal atoms M, of the formulaII′

wherein W is selected from O, S, NR₄ and CR₅R₆, X is N or CH, Y isselected from O, S and NR₈; R₁ and R₂ independently are H, unsubstitutedor substituted C₁-C₁₈alkyl, unsubstituted or substituted C₂-C₁₈alkenyl,unsubstituted or substituted C₅-C₁₀aryl, unsubstituted or substitutedC₅-C₁₀heteroaryl, C₁-C₁₈acyl, halogen, C₁-C₁₈alkoxy, C₁-C₁₈alkylthio,C₃-C₁₂cycloalkyl, C₁-C₁₈acyloxy, C₅-C₁₀aryloxy, C₃-C₁₂cycloalkyloxy,COR, CH═NR, CH═N—OH, CH═N—OR, COOR, CONHR, CONRR′, CONH—NHR, CONH—NRR′,SO₂R, SO₃R, SO₂NHR, SO₂NRR′, SO₂NH—NHR, SO₂NH—NRR′, S(O)R, S(O)OR,S(O)NHR, S(O)NRR′, S(O)NH—NHR, S(O)NH—NRR′, SiRR′R″, PORR′, PO(OR)R′,PO(OR)₂, PO(NHR)₂, PO(NRR′)₂, CN, NO₂, NHR, NRR′, NH—NHR, NH—NRR′ orCONROH; R is H, C₁-C₁₂alkyl, C₅-C₁₀aryl or C₃-C₁₂cycloalkyl, R′ and R″independently are selected from C₁-C₁₂alkyl, C₅-C₁₀aryl andC₃-C₁₂cycloalkyl, or neighbouring residues R₁ and R₂ form an organicbridging group completing, together with the carbon atoms they arebonding to, a carbocyclic or heterocyclic, non-aromatic or aromatic ringof 5 to 7 ring atoms in total, which optionally may be substituted; R₄,R₅, R₆ independently are H, unsubstituted or substituted C₁-C₁₈alkyl,unsubstituted or substituted C₂-C₁₈alkenyl, unsubstituted or substitutedC₅-C₁₀aryl, unsubstituted or substituted C₂-C₁₀heteroaryl, C₁-C₁₈acyl;R₃ is H, unsubstituted or substituted C₁-C₁₈alkyl, unsubstituted orsubstituted C₂-C₁₈alkenyl, unsubstituted or substituted C₅-C₁₀aryl,unsubstituted or substituted C₂-C₁₀heteroaryl, C₁-C₁₈acyl, OR, SR, NRR′,or is C₂-C₅alkynyl, C₃-C₅cycloalkyl, hetero-C₂-C₅cycloalkyl orC₃-C₅cycloalkenyl each unsubstituted or mono- or poly-substituted byCOR, COOR, CONRR′, CN, halogen and/or by OR; R′₃ is unsubstituted orsubstituted C₁-C₁₈alkylene, unsubstituted or substitutedC₂-C₁₈alkenylene, unsubstituted or substituted C₅-C₁₀arylene,unsubstituted or substituted C₂-C₁₀heteroarylene or C₂-C₁₈diacylene; andR₈ is hydrogen or a substituent.
 2. Compound of claim 1, wherein formulaI is formula (III) or tautomeric forms thereof,

wherein

is a bidentate C,N-binding ligand, CyC and CyN are interlinked by achemical bond, n is 1, M is Ir and m is 2 or M is Pt and m is 1; W is O,S, NR₄, CR₅R₆, X is N or CH, Y is O or NR₈; R₁, R₂ independently areselected from H, C₁-C₈alkyl, phenyl, halogen, C₁-C₈alkoxy, CN, NHR,NRR′; or R₁ and R₂ together with the carbon atoms they are bonding toform an annellated phenyl ring, which optionally may be substituted; R₃is H, unsubstituted or substituted C₁-C₈alkyl, unsubstituted orsubstituted C₂-C₈alkenyl, unsubstituted or substituted phenyl; R₄, R₅,R₆ independently are H or C₁-C₈alkyl; R₈ is H, C₁-C₈alkyl, COR, SO₂R;and R and R′ independently are selected from C₁-C₆alkyl, and R may alsobe hydrogen.
 3. Compound of claim 2, wherein

is


4. Compound of claim 1 of formula (I) or (I′) wherein Y is O or NR₈; Mis selected from Tl, Pb, Bi, In, Sn, Sb, Te, Mo, Cr, Mn, Ta, V, Cu, Fe,Ru, Ni, Co, Ir, Pt, Pd, Rh, Re, Os, Ag and Au; R₁, R₂, R₃, R₄, R₅, R₆,R₈ are as defined above and, if substituted, the substituent is selectedfrom halogen, C₁-C₁₂alkoxy, C₁-C₁₂alkylthio, benzoyl substituted byC₁-C₄alkyl or C₁-C₄alkoxy or halogen, benzoyloxy substituted byC₁-C₄alkyl or C₁-C₄alkoxy or halogen, phenyl, phenyloxy,C₃-C₁₂cycloalkyl, C₃-C₁₂cycloalkyloxy, or from the residues COR, OCOR,COOR, CONHR, CONRR′, SO₂R, SO₃R, SO₂NHR, SO₂NRR′, SiRR′R″, PORR′,PO(OR)R′, PO(OR)₂, CN, NO₂, NHR, NRR′, NH—NHR, NH—NRR′, where R, R′ andR″ independently are selected from C₁-C₁₂alkyl, C₁-C₆haloalkyl, phenyl,cyclopentyl, cyclohexyl; and R may also be hydrogen.
 5. Compoundaccording to claim 1, wherein L is selected from the ligands: a) offormula

wherein R⁶, R⁷, R⁸, and R⁹ are independently of each other hydrogen,C₁-C₂₄alkyl, C₂-C₂₄alkenyl, C₂-C₂₄alkynyl, aryl, heteroaryl,C₁-C₂₄alkoxy, C₁-C₂₄alkylthio, cyano, acyl, alkyloxycarbonyl, a nitrogroup, or a halogen atom; or two substituents R⁶, R⁷, R⁸, and R⁹, whichare adjacent to each other, together form a group

wherein R²⁰⁵, R²⁰⁶, R²⁰⁷ and R²⁰⁸ are independently of each other H, orC₁-C₈alkyl, the ring A represents an optionally substituted aryl orheteroaryl group; or the ring A may be taken with the pyridyl groupbinding to the ring A to form a ring; the alkyl group, alkenyl group,alkynyl group, aryl group, heteroaryl group, alkoxy group, alkylthiogroup, acyl group, and alkyloxycarbonyl group represented by R⁶, R⁷, R⁸,and R⁹ may be substituted; b) of formula

wherein Y′ is S, O, NR²⁰⁰, wherein R²⁰⁰ is hydrogen, cyano, C₁-C₄alkyl,C₂-C₄alkenyl, C₆-C₁₀aryl, —(CH₂)_(r)—Ar wherein Ar is C₆-C₁₀aryl, agroup —(CH₂)_(r′)X²⁰, wherein r′ is an integer of 1 to 5, X²⁰ ishalogen, hydroxy, —O—C₁-C₄alkyl, di(C₁-C₄alkyl)amino, amino, or cyano; agroup —(CH₂)_(r)OC(O)(CH₂)r″CH₃, wherein r is 1, or 2, and r″ is 0, or1;

—NH-Ph, —C(O)CH₃, —CH₂—O—(CH₂)₂—Si(CH₃)₃, or

c) of formula

wherein Q¹ and Q² are independently of each other hydrogen, C₁-C₂₄alkyl,or C₆-C₁₈aryl, A²¹ is hydrogen, halogen, C₁-C₄alkoxy, or C₁-C₄alkyl, A²²is hydrogen, halogen, C₁-C₁₂alkoxy, C₁-C₁₂alkyl, or C₆-C₁₀aryl, A²³ ishydrogen, halogen, C₁-C₁₂alkoxy, C₁-C₁₂alkyl, or C₆-C₁₀aryl, A²⁴ ishydrogen, halogen, C₁-C₄alkoxy, or C₁-C₄alkyl, or A²² and A²³, or A²³and A²⁴ together form a group

wherein R²⁰⁵, R²⁰⁶, R²⁰⁷ and R²⁰⁸ are independently of each other H,halogen, C₁-C₁₂alkoxy, or C₁-C₁₂alkyl, R⁴² is H, halogen, C₁-C₁₂alkyl,C₁-C₁₂alkoxy, or C₁-C₄perfluoroalkyl, R⁴³ is H, halogen, C₁-C₁₂alkyl,C₁-C₁₂alkoxy, C₁-C₄perfluoroalkyl, C₇-C₁₅aralkyl, or C₆-C₁₀aryl, R⁴⁴ isH, halogen, C₁-C₁₂alkyl, C₁-C₁₂alkoxy, C₆-C₁₀aryl, C₇-C₁₅aralkyl, orC₁-C₄perfluoroalkyl, R⁴⁵ is H, halogen, C₁-C₁₂alkyl, C₁-C₁₂alkoxy, orC₁-C₄perfluoroalkyl; d1) of formula

wherein n is 0, 1 or 2; A¹², A¹⁴, A¹⁶, A²¹, A²², A²³, and A²⁴ areindependently of each other hydrogen, CN, halogen, C₁-C₂₄alkyl,C₁-C₂₄alkoxy, C₁-C₂₄alkylthio, C₁-C₂₄perfluoroalkyl, C₆-C₁₈aryl, whichis optionally substituted by G; —NR²⁵R²⁶, —CONR²⁵R²⁶, or —COOR²⁷, orC₂-C₁₀heteroaryl, which is optionally substituted by G; orC₅-C₁₂cycloalkyl, C₅-C₁₂cycloalkoxy, C₅-C₁₂cycloalkylthio, each of whichis optionally substituted by G; 2 adjacent radicals A¹⁴, A¹⁷ or A¹⁷,A¹⁶, bonding to vicinal atoms, together are a group of formula

wherein A⁴¹, A⁴², A⁴³, A⁴⁴, A⁴⁵, and A⁴⁶ are independently of each otherH, halogen, CN, C₁-C₂₄alkyl, C₁-C₂₄perfluoroalkyl, C₁-C₂₄alkoxy,C₁-C₂₄alkylthio, C₆-C₁₈aryl, which may optionally be substituted by G,—NR²⁵R²⁶, —CONR²⁵R²⁶, or —COOR²⁷, or C₂-C₁₀heteroaryl; A¹¹, A¹³, A¹⁵,A′²¹, A′²², A′²³, and A′²⁴ are independently of each other is hydrogenor C₁-C₂₄alkyl; or 2 adjacent radicals A¹¹, A¹²; A¹³, A¹⁴; A¹⁵, A¹⁶;A′²¹, A²¹; A′²², A²²; A′²³, A²³; A′²⁴, A²⁴, bonding to the same carbonatom, together are ═O or ═NR²⁵ or ═N—OR²⁵ or ═N—OH; R²⁵ and R²⁶ areindependently of each other C₆-C₁₈aryl, C₇-C₁₅aralkyl, or C₁-C₂₄alkyl,R²⁷ is C₁-C₂₄alkyl, C₆-C₁₈aryl, or C₇-C₁₈aralkyl; or d2) of the formula

wherein A′²² and A′²³ are independently of each other hydrogen orC₁-C₂₄alkyl; 2 adjacent radicals A¹⁸, A²² and A²³, A¹⁹, bonding tovicinal atoms, together are a group of formula

wherein A⁴¹, A⁴², A⁴³, A⁴⁴, A⁴⁵, and A⁴⁶ are independently of each otherH, halogen, CN, C₁-C₂₄alkyl, C₁-C₂₄perfluoroalkyl, C₁-C₂₄alkoxy,C₁-C₂₄alkylthio, C₆-C₁₈aryl, which may optionally be substituted by G,—NR²⁵R²⁶, —CONR²⁵R²⁶, or —COOR²⁷, or C₂-C₁₀heteroaryl; R²⁵ and R²⁶ areindependently of each other C₆-C₁₈aryl, C₇-C₁₈aralkyl, or C₁-C₂₄alkyl,R²⁷ is C₁-C₂₄alkyl, C₆-C₁₈aryl, or C₇-C₁₈aralkyl; and for d1) and d2):Y¹, Y² and Y³ are independently of each other a group of formula

wherein R⁴¹ is the bond to M, R⁷¹ is the bond to M, R⁴² is hydrogen,C₁-C₂₄alkyl, CN, C₁-C₂₄alkyl, which is substituted by halogen,C₆-C₁₈-aryl, C₆-C₁₈-aryl substituted by C₁-C₁₂alkyl, or C₁-C₈alkoxy, R⁴³is hydrogen, CN, halogen, C₁-C₂₄alkyl substituted by F, C₆-C₁₈aryl,C₆-C₁₈aryl substituted by C₁-C₁₂alkyl, or C₁-C₈alkoxy, —CONR²⁵R²⁶,—COOR²⁷,

wherein E² is —S—, —O—, or —NR^(25′)—, wherein R^(25′) is C₁-C₂₄alkyl,or C₆-C₁₀aryl, or R⁴² and R⁴³ are a group of formula

wherein A⁴¹, A⁴², A⁴³, A⁴⁴, A⁴⁵, and A⁴⁶ are independently of each otherH, halogen, CN, C₁-C₂₄alkyl, C₁-C₂₄perfluoroalkyl, C₁-C₂₄alkoxy,C₁-C₂₄alkylthio, C₆-C₁₈aryl, which may optionally be substituted by G,—NR²⁵R²⁶, —CONR²⁵R²⁶, or —COOR²⁷, or C₂-C₁₀heteroaryl; R⁴⁴ is hydrogen,CN, C₁-C₂₄alkyl, C₁-C₂₄alkyl substituted by F, halogen, C₆-C₁₈-aryl,C₆-C₁₈-aryl substituted by C₁-C₁₂ alkyl, or C₁-C₈alkoxy, R⁴⁵ ishydrogen, CN, C₁-C₂₄alkyl, C₁-C₂₄alkyl substituted by F, halogen,C₆-C₁₈-aryl, C₆-C₁₈-aryl substituted by C₁-C₁₂alkyl, or C₁-C₈alkoxy,A^(11′), A^(12′), A^(13′) and A^(14′) are independently of each other H,halogen, CN, C₁-C₂₄alkyl, C₁-C₂₄alkoxy, C₁-C₂₄alkylthio, —NR²⁵R²⁶,—CONR²⁵R²⁶, or —COOR²⁷, R⁶⁸ and R⁶⁹ are independently of each otherC₁-C₂₄alkyl, which may be interrupted by one or two oxygen atoms, R⁷⁰,R⁷², R⁷³, R⁷⁴, R⁷⁵, R⁷⁶, R⁹⁰, R⁹¹, R⁹², and R⁹³ are independently ofeach other H, halogen, CN, C₁-C₂₄alkyl, C₆-C₁₀aryl, C₁-C₂₄alkoxy,C₁-C₂₄alkylthio, —NR²⁵, R²⁶, —CONR²⁵R²⁶, or —COOR²⁷, wherein R²⁵, R²⁶and R²⁷ are as defined above and G is C₁-C₁₈alkyl, —OR³⁰⁵, —SR³⁰⁵,—NR³⁰⁵R³⁰⁶, —CONR³⁰⁵R³⁰⁶, or —CN, wherein R³⁰⁵ and R³⁰⁶ areindependently of each other C₆-C₁₈aryl; C₆-C₁₈aryl which is substitutedby C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl, or C₁-C₁₈alkyl which isinterrupted by —O—; or R³⁰⁵ and R³⁰⁶ together form

e) of formula

wherein R⁶ is hydrogen, halogen, nitro, C₁-C₄alkyl, C₁-C₄perfluoroalkyl,C₁-C₄alkoxy, or C₆-C₁₀aryl, R⁷ is hydrogen, halogen, C₁-C₄alkyl,C₁-C₄perfluoroalkyl, C₆-C₁₀aryl, C₆-C₁₀perfluoroaryl, R⁸ is hydrogen,C₁-C₄alkyl, C₁-C₈alkoxy, C₁-C₄perfluoroalkyl, C₆-C₁₀aryl,C₆-C₁₀perfluoroaryl, R⁹ is hydrogen, halogen, nitro, cyano, C₁-C₄alkyl,C₁-C₄perfluoroalkyl, C₁-C₄alkoxy, or C₆-C₁₀aryl, A¹⁰ is hydrogen,halogen, nitro, cyano, C₁-C₄alkyl, C₂-C₄alkenyl, C₁-C₄perfluoroalkyl,—O—C₁-C₄perfluoroalkyl, tri(C₁-C₄alkyl)silanyl, C₆-C₁₀aryl, orC₆-C₁₀perfluoroaryl, A¹¹ is hydrogen, halogen, nitro, cyano, C₁-C₄alkyl,C₂-C₄alkenyl, C₁-C₄perfluoroalkyl, —O—C₁-C₄perfluoroalkyl,tri(C₁-C₄alkyl)silanyl, C₆-C₁₀aryl, or C₆-C₁₀perfluoroaryl, A¹² ishydrogen, halogen, nitro, hydroxy, mercapto, amino, C₁-C₄alkyl,C₂-C₄alkenyl, C₁-C₄perfluoroalkyl, C₁-C₄alkoxy, —O—C₁-C₄perfluoroalkyl,—S—C₁-C₄alkyl, a group —(CH₂)_(r)X²⁰, wherein r is 1, or 2, X²⁰ ishalogen, hydroxy, cyano, —O—C₁-C₄alkyl, di(C₁-C₄alkyl)amino, —CO₂X²¹,wherein X²¹ is H, or C₁-C₄alkyl; —CH═CHCO₂X²², wherein X²² isC₁-C₄alkyl; —CH(O), —SO₂X²³, —SOX²³, —NC(O)X²³, —NSO₂X²³, —NHX²³,—N(X²³)₂, wherein X²³ is C₁-C₄alkyl; tri(C₁-C₄alkyl)siloxanyl,—O—C₆-C₁₀aryl, cyclohexyl, C₆-C₁₀aryl, or C₆-C₁₀perfluoroaryl, and A¹³is hydrogen, nitro, cyano, C₁-C₄alkyl, C₂-C₄alkenyl,C₁-C₄perfluoroalkyl, —O—C₁-C₄perfluoroalkyl, tri(C₁-C₄alkyl)silanyl, orC₆-C₁₀aryl.
 6. Compound of claim 1, wherein n is an integer 1, M is Co,Fe, Ir or Rh, and m is 2, or M is Ni, Rh, Ru, Pd or Pt, and m is 1, R₁,R₂ independently are selected from H, unsubstituted or substitutedC₁-C₈alkyl, unsubstituted or substituted phenyl, halogen, C₁-C₈alkoxy,COR, COOR, SO₂R, CN, NHR and NRR′; or the neighbouring residues R₁ andR₂ form an organic bridging group completing, together with the carbonatoms they are bonding to, an annellated phenyl ring, which optionallymay be substituted; R₅, R₆ independently are unsubstituted orsubstituted C₁-C₈alkyl, unsubstituted or substituted C₂-C₈alkenyl,unsubstituted or substituted phenyl; R₄ is as defined for R₅ or ishydrogen; R₃ is unsubstituted or substituted C₁-C₈alkyl, unsubstitutedor substituted C₂-C₈alkenyl, unsubstituted or substituted phenyl; andany substituent, if present, is selected from halogen, C₁-C₈alkyl,C₁-C₈alkoxy, phenyl, phenyloxy, COR, OCOR, COOR, SO₂R, CN, NHR, NRR′;and R and R′ independently are selected from C₁-C₆alkyl, and R may alsobe hydrogen; R₈ is H, SO₂—R₁₁, CO—R₁₁, where R₁₁ is C₁-C₁₂alkyl,C₁-C₁₂haloalkyl, phenyl, phenyl substituted by halogen.
 7. An organicelectronic device comprising an emitting layer wherein the emittinglayer comprises a compound according to claim
 1. 8. The device of claim7, further comprising a hole transport layer selected frompolyvinyl-carbazol, N, N′-diphenyl-N,N′-bis(3-methylphenyl)-[1,1′-biphenyl]-4,4′-diamine (TPD),1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC),N,N′-bis(4-methylphenyl)-N,N′-bis(4-ethylphenyl)-[1,1′-(3,3′-dimethyl)biphenyl]4,4′-diamine(ETPD), tetrakis-(3-methylphenyl)-N,N,N′,N′-2,5-phenylenediamine (PDA),a-phenyl-4-N,N-diphenylaminostyrene (TPS),p-(diethylamino)benzaldehydediphenylhydrazone (DEH), triphenylamine(TPA), bis[4-(N,N-diethylamino)-2-methylphenyl](4-methylphenyl)methane(MPMP),1-phenyl-3-[p-(diethylamino)styryl]-5-[p-(diethylamino)phenyl]pyrazoline(PPR or DEASP), 1,2-trans-bis (9H-carbazol-9-yl)cyclobutane (DCZB),N,N,N′,N′-tetrakis (4-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine (TTB),4,4′-N,N-dicarbazole-biphenyl (CBP),N,N-dicarbazoyl-1,4-dimethene-benzene (DCB), porphyrinic compounds, andcombinations thereof.
 9. A compound of formula (III) or tautomeric formsthereof,

wherein

is a bidentate C,N-binding ligand, CyC and CyN are interlinked by achemical bond, n is 1, M is Ir and m is 2 or M is Pt and m is 1; andwherein the moiety

is selected from a group consisting of


10. Compound of claim 1, wherein formula (I′) is

with n=2.
 11. Compound of the formula I[LDH]_(n)M[L]_(m)  (I), wherein n is an integer 1, M is Co, Fe, Ir, orRh, and m is 2, or M is Ni, Rh, Ru, Pd, or Pt, and m is 1, LDH is abidentate ligand of the formula II

wherein W is selected from O, S, NR₄, CR₅R₆, X is N or CH, Y is selectedfrom O, S, NR₈; R₁, R₂ independently are selected from H, unsubstitutedor substituted C₁-C₈alkyl, unsubstituted or substituted phenyl, halogen,C₁-C₈alkoxy, COR, COOR, SO₂R, CN, NHR, NRR′; or the neighbouringresidues R₁ and R₂ form an organic bridging group completing, togetherwith the carbon atoms they are bonding to, an annellated phenyl ring,which optionally may be substituted; R₄, R₅, R₆ independently are H,unsubstituted or substituted C₁-C₈alkyl, unsubstituted or substitutedC₂-C₈alkenyl, unsubstituted or substituted phenyl; R₃ is H,unsubstituted or substituted C₁-C₈alkyl, unsubstituted or substitutedC₂-C₈alkenyl, unsubstituted or substituted phenyl; and any substituent,if present, is selected from halogen, C₁-C₈alkyl, C₁-C₈alkoxy, phenyl,phenyloxy, COR, OCOR, COOR, SO₂R, CN, NHR, NRR′; and R and R′independently are selected from C₁-C₆alkyl, and R may also be hydrogen;R₈ is H, SO₂—R₁₁, CO—R₁₁, where R_(ii) is C₁-C₁₂alkyl, C₁-C₁₂haloalkyl,phenyl, phenyl substituted by halogen; and L is a bidentate ligand andis selected from the ligands: a) of formula

wherein R⁶, R⁷, R⁸, and R⁹ are independently of each other hydrogen,C₁-C₂₄alkyl, C₂-C₂₄alkenyl, C₂-C₂₄alkynyl, aryl, heteroaryl,C₁-C₂₄alkoxy, C₁-C₂₄alkylthio, cyano, acyl, alkyloxycarbonyl, a nitrogroup, or a halogen atom; or two R⁶, R⁷, R⁸, and R⁹, which are adjacentto each other, together form a group

wherein R²⁰⁵, R²⁰⁶, R²⁰⁷ and R²⁰⁸ are independently of each other H, orC₁-C₈alkyl, the ring A represents an optionally substituted aryl orheteroaryl group; or the ring A may be taken with the pyridyl groupbinding to the ring A to form a ring; the alkyl group, alkenyl group,alkynyl group, aryl group, heteroaryl group, alkoxy group, alkylthiogroup, acyl group, and alkyloxycarbonyl group represented by R⁶, R⁷, R⁸,and R⁹ may be substituted; b) of the formula

wherein Y′ is S, O, NR²⁰⁰, wherein R²⁰⁰ is hydrogen, cyano, C₁-C₄alkyl,C₂-C₄alkenyl, optionally substituted C₆-C₁₀aryl, —(CH₂)_(r)—Ar whereinAr is an optionally substituted C₆-C₁₀aryl, a group —(CH₂)_(r′)X²⁰,wherein r′ is an integer of 1 to 5, X²⁰ is halogen, hydroxy,—O—C₁-C₄alkyl, di(C₁-C₄alkyl)amino, amino, or cyano; a group—(CH₂)_(r)OC(O)(CH₂)r″CH₃, wherein r is 1, or 2, and r″ is 0, or 1;

—NH-Ph, —C(O)CH₃, —CH₂—O—(CH₂)₂—Si(CH₃)₃, or

c) of the formula

wherein Q¹ and Q² are independently of each other hydrogen, C₁-C₂₄alkyl,or C₆-C₁₈aryl, A²¹ is hydrogen, halogen, C₁-C₄alkoxy, or C₁-C₄alkyl, A²²is hydrogen, halogen, C₁-C₁₂alkoxy, C₁-C₁₂alkyl, or C₆-C₁₀aryl, A²³ ishydrogen, halogen, C₁-C₁₂alkoxy, C₁-C₁₂alkyl, or C₆-C₁₀aryl, A²⁴ ishydrogen, halogen, C₁-C₄alkoxy, or C₁-C₄alkyl, or A²² and A²³, or A²³and A²⁴ together form a group

wherein R²⁰⁵, R²⁰⁶, R²⁰⁷ and R²⁰⁸ are independently of each other H,halogen, C₁-C₁₂alkoxy, or C₁-C₁₂alkyl, R⁴² is H, halogen, C₁-C₁₂alkyl,C₁-C₁₂alkoxy, or C₁-C₄perfluoroalkyl, R⁴³ is H, halogen, C₁-C₁₂alkyl,C₁-C₁₂alkoxy, C₁-C₄perfluoroalkyl, C₇-C₁₅aralkyl, or C₆-C₁₀aryl, R⁴⁴ isH, halogen, C₁-C₁₂alkyl, C₁-C₁₂alkoxy, C₆-C₁₀aryl, C₇-C₁₅aralkyl, orC₁-C₄perfluoroalkyl, R⁴⁵ is H, halogen, C₁-C₁₂alkyl, C₁-C₁₂alkoxy, orC₁-C₄perfluoroalkyl; d1) of the formula

wherein n is 0, 1 or 2, A¹², A¹⁴, A¹⁶, A²¹, A²², A²³, and A²⁴ areindependently of each other hydrogen, CN, halogen, C₁-C₂₄alkyl,C₁-C₂₄alkoxy, C₁-C₂₄alkylthio, C₁-C₂₄perfluoroalkyl, C₆-C₁₈aryl, whichis optionally substituted by G; —NR²⁵R²⁶, —CONR²⁵R²⁶, or —COOR²⁷, orC₂-C₁₀heteroaryl, which is optionally substituted by G; orC₅-C₁₂cycloalkyl, C₅-C₁₂cycloalkoxy, C₅-C₁₂cycloalkylthio, each of whichis optionally substituted by G; 2 adjacent radicals A¹⁴, A¹⁷ or A¹⁷,A¹⁶, bonding to vicinal atoms, together are a group of formula

wherein A⁴¹,A⁴², A⁴³, A⁴⁴, A⁴⁵, and A⁴⁶ are independently of each otherH, halogen, CN, C₁-C₂₄alkyl, C₁-C₂₄perfluoroalkyl, C₁-C₂₄alkoxy,C₁-C₂₄alkylthio, C₆-C₁₈aryl, which may optionally be substituted by G,—NR²⁵R²⁶, —CONR²⁵R²⁶, or —COOR²⁷, or C₂-C₁₀heteroaryl; A¹¹, A¹³, A¹⁵,A′²¹, A′²², A′²³ and A′²⁴ are independently of each other hydrogen orC₁-C₂₄alkyl; or 2 adjacent radicals A¹¹, A¹²; A¹³, A¹⁴; A¹⁵, A¹⁶; A′²¹,A²¹; A′²², A²²; A′²³, A²³; A′²⁴, A²⁴, bonding to the same carbon atom,together are ═O or ═NR²⁵ or ═N—OR²⁵ or ═N—OH; R²⁵ and R²⁶ areindependently of each other C₆-C₁₈aryl, C₇-C₁₈aralkyl, or C₁-C₂₄alkyl,R²⁷ is C₁-C₂₄alkyl, C₆-C₁₈aryl, or C₇-C₁₈aralkyl; or d2) of the formula

wherein A′²² and A′²³ are independently of each other hydrogen orC₁-C₂₄alkyl; 2 adjacent radicals A¹⁸, A²² and A²³, A¹⁹, bonding tovicinal atoms, together are a group of formula

wherein A⁴¹, A⁴², A⁴³, A⁴⁴, A⁴⁵, and A⁴⁶ are independently of each otherH, halogen, CN, C₁-C₂₄alkyl, C₁-C₂₄perfluoroalkyl, C₁-C₂₄alkoxy,C₁-C₂₄alkylthio, C₆-C₁₈aryl, which may optionally be substituted by G,—NR²⁵R²⁶, —CONR²⁵R²⁶, or —COOR²⁷, or C₂-C₁₀heteroaryl; R²⁵ and R²⁶ areindependently of each other C₆-C₁₈aryl, C₇-C₁₈aralkyl, or C₁-C₂₄alkyl,R²⁷ is C₁-C₂₄alkyl, C₆-C₁₈aryl, or C₇-C₁₈aralkyl; and for d1) and d2):Y¹, Y² and Y³ are independently of each other a group of formula

wherein R⁴¹ is the bond to M, R⁷¹ is the bond to M, R⁴² is hydrogen, orC₁-C₂₄alkyl, CN, C₁-C₂₄alkyl, which is substituted by halogen,C₆-C₁₈-aryl, C₆-C₁₈-aryl substituted by C₁-C₁₂alkyl, or C₁-C₈alkoxy, R⁴³is hydrogen, CN, halogen, C₁-C₂₄alkyl substituted by F, C₆-C₁₈aryl,C₆-C₁₈aryl substituted by C₁-C₁₂alkyl, or C₁-C₈alkoxy, —CONR²⁵R²⁶,—COOR²⁷,

wherein E² is —S—, —O—, or —NR^(25′)—, wherein R^(25′) is C₁-C₂₄alkyl,or C₆-C₁₀aryl, or R⁴² and R⁴³ are a group of formula

wherein A⁴¹, A⁴², A⁴³, A⁴⁴, A⁴⁵, and A⁴⁶ are independently of each otherH, halogen, CN, C₁-C₂₄alkyl, C₁-C₂₄perfluoroalkyl, C₁-C₂₄alkoxy,C₁-C₂₄alkylthio, C₆-C₁₈aryl, which may optionally be substituted by G,—NR²⁵R²⁶, —CONR²⁵R²⁶, or —COOR²⁷, or C₂-C₁₀heteroaryl; R⁴⁴ is hydrogen,CN or C₁-C₂₄alkyl, C₁-C₂₄alkyl substituted by F, halogen, C₆-C₁₈-aryl,C₆-C₁₈-aryl substituted by C₁-C₁₂ alkyl, or C₁-C₈alkoxy, R⁴⁵ ishydrogen, CN or C₁-C₂₄alkyl, C₁-C₂₄alkyl substituted by F, halogen,C₆-C₁₈-aryl, C₆-C₁₈-aryl substituted by C₁-C₁₂alkyl, or C₁-C₈alkoxy,A^(11′), A^(12′), A^(13′), and A^(14′) are independently of each otherH, halogen, CN, C₁-C₂₄alkyl, C₁-C₂₄alkoxy, C₁-C₂₄alkylthio, —NR²⁵R²⁶,—CONR²⁵R²⁶, or —COOR²⁷, R⁶⁸ and R⁶⁹ are independently of each otherC₁-C₂₄alkyl, which may be interrupted by one or two oxygen atoms, R⁷⁰,R⁷², R⁷³, R⁷⁴, R⁷⁵, R⁷⁶, R⁹⁰, R⁹¹, R⁹², and R⁹³ are independently ofeach other H, halogen, CN, C₁-C₂₄alkyl, C₆-C₁₀aryl, C₁-C₂₄alkoxy,C₁-C₂₄alkylthio, —NR²⁵R²⁶, —CONR²⁵R²⁶, or —COOR²⁷, wherein R²⁵, R²⁶ andR²⁷ are as defined above and G is C₁-C₁₈alkyl, —OR³⁰⁵, —SR³⁰⁵,—NR³⁰⁵R³⁰⁶, —CONR³⁰⁵R³⁰⁶, or —CN, wherein R³⁰⁵ and R³⁰⁶ areindependently of each other C₆-C₁₈aryl; C₆-C₁₈aryl which is substitutedby C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl, or C₁-C₁₈alkyl which isinterrupted by —O—; or R³⁰⁵ and R³⁰⁶ together form a five or sixmembered ring; e) of formula

wherein R⁶ is hydrogen, halogen, nitro, C₁-C₄alkyl, C₁-C₄perfluoroalkyl,C₁-C₄alkoxy, or optionally substituted C₆-C₁₀aryl, R⁷ is hydrogen,halogen, C₁-C₄alkyl, C₁-C₄perfluoroalkyl, optionally substitutedC₆-C₁₀aryl, or optionally substituted C₆-C₁₀perfluoroaryl, R⁸ ishydrogen, C₁-C₄alkyl, C₁-C₈alkoxy, C₁-C₄perfluoroalkyl, optionallysubstituted C₆-C₁₀aryl, or optionally substituted C₆-C₁₀perfluoroaryl,R⁹ is hydrogen, halogen, nitro, cyano, C₁-C₄alkyl, C₁-C₄perfluoroalkyl,C₁-C₄alkoxy, or optionally substituted C₆-C₁₀aryl, A¹⁰ is hydrogen,halogen, nitro, cyano, C₁-C₄alkyl, C₂-C₄alkenyl, C₁-C₄perfluoroalkyl,—O—C₁-C₄perfluoroalkyl, tri(C₁-C₄alkyl)silanyl, optionally substitutedC₆-C₁₀aryl, or optionally substituted C₆-C₁₀perfluoroaryl, A¹¹ ishydrogen, halogen, nitro, cyano, C₁-C₄alkyl, C₂-C₄alkenyl,C₁-C₄perfluoroalkyl, —O—C₁-C₄perfluoroalkyl, tri(C₁-C₄alkyl)silanyl,optionally substituted C₆-C₁₀aryl, or optionally substitutedC₆-C₁₀perfluoroaryl, A¹² is hydrogen, halogen, nitro, hydroxy, mercapto,amino, C₁-C₄alkyl, C₂-C₄alkenyl, C₁-C₄perfluoroalkyl, C₁-C₄alkoxy,—O—C₁-C₄perfluoroalkyl, —S—C₁-C₄alkyl, a group —(CH₂)_(r)X²⁰, wherein ris 1, or 2, X²⁰ is halogen, hydroxy, cyano, —O—C₁-C₄alkyl,di(C₁-C₄alkyl)amino, —CO₂X²¹, wherein X²¹ is H, or C₁-C₄alkyl;—CH═CHCO₂X²², wherein X²² is C₁-C₄alkyl; —CH(O), —SO₂X²³, —SOX²³,—NC(O)X²³, —NSO₂X²³, —NHX²³, —N(X²³)₂, wherein X²³ is C₁-C₄alkyl;tri(C₁-C₄alkyl)siloxanyl, optionally substituted —O—C₆-C₁₀aryl,cyclohexyl, optionally substituted C₆-C₁₀aryl, or optionally substitutedC₆-C₁₀perfluoroaryl, and A¹³ is hydrogen, nitro, cyano, C₁-C₄alkyl,C₂-C₄alkenyl, C₁-C₄perfluoroalkyl, —O—C₁-C₄perfluoroalkyl,tri(C₁-C₄alkyl)silanyl, or optionally substituted C₆-C₁₀aryl.
 12. Thecompound according to claim 11, wherein n is an integer 1, M is Ir, orRh, and m is
 2. 13. The compound according to claim 11, wherein n is aninteger 1, M is Pd, or Pt, and m is
 1. 14. The compound according toclaim 11, wherein L is a ligand of formula

wherein A²¹, A²², A²³, A²⁴, R⁴², R⁴³, R⁴⁴ and R⁴⁵ are as defined for c)in claim
 11. 15. The compound according to claim 11, which is a compoundof formula

wherein

is a bidentate ligand L, L is as defined in claim 11, n is 1, M is Irand m is 2, or M is Pt and m is 1; W is O, S, NR₄, CR₅R₆, X is N or CH,Y is O or NR₈; R₁, R₂ independently are selected from H, C₁-C₈alkyl,phenyl, halogen, C₁-C₈alkoxy, CN, NHR, NRR′; or R₁ and R₂ together withthe carbon atoms they are bonding to form an annellated phenyl ring,which optionally may be substituted; R₃ is H, unsubstituted orsubstituted C₁-C₈alkyl, unsubstituted or substituted C₂-C₈alkenyl,unsubstituted or substituted phenyl; R₄, R₅, R₆ independently are H orC₁-C₈alkyl; R₈ is H, SO₂—R₁₁, CO—R₁₁, where R₁₁ is C₁-C₁₂alkyl,C₁-C₁₂haloalkyl, phenyl, phenyl substituted by halogen; and anysubstituent, if present, is selected from halogen, C₁-C₈alkyl,C₁-C₈alkoxy, COR, NHR, NRR′; and R and R′ independently are selectedfrom C₁-C₆alkyl, and R may also be hydrogen.
 16. An organic electronicdevice comprising an emitting layer wherein the emitting layer comprisesa compound according to claim
 11. 17. The organic electronic deviceaccording to claim 16, which is an organic light emitting diode.
 18. Thedevice of claim 17, further comprising a hole transport layer selectedfrom the group consisting of polyvinyl-carbazol, N, N′-diphenyl-N,N′-bis(3-methylphenyl)-[1,1′-biphenyl]-4,4′-diamine (TPD),1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC),N,N′-bis(4-methylphenyl)-N,N′-bis(4-ethylphenyl)-[1,1′-(3,3′-dimethyl)biphenyl]4,4′-diamine(ETPD), tetrakis-(3-methylphenyl)-N,N,N′,N′-2,5-phenylenediamine (PDA),a-phenyl-4-N,N-diphenylaminostyrene (TPS),p-(diethylamino)benzaldehydediphenylhydrazone (DEH), triphenylamine(TPA), bis[4-(N,N-diethylamino)-2-methylphenyl](4-methylphenyl)methane(MPMP),1-phenyl-3-[p-(diethylamino)styryl]-5-4)-(diethylamino)phenyllpyrazoline(PPR or DEASP), 1,2-trans-bis (9H-carbazol-9-yl)cyclobutane (DCZB),N,N,N′,N′-tetrakis (4-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine (TTB),4,4′-N,N-dicarbazole-biphenyl (CBP),N,N-dicarbazoyl-1,4-dimethene-benzene (DCB), porphyrinic compounds, andcombinations thereof.
 19. A stationary display or a mobile displaycomprising the organic light emitting diode according to claim
 17. 20. Amethod of using the compound according to claim 11 in an electronicdevice comprising: adding the compound according to claim 11 in anemitting layer in the electronic device.